Contemporary Methods For The Experimental Determination of Dissociation Constants of Organic Acids in Solutions - Russs - J - Gen - Chen

ISSN 1070-3632, Russian Journal of General Chemistry, 2009, Vol. 79, No. 9, pp. 18591889. Pleiades Publishing, Ltd.
., 2009. Original Russian Text Yu.E. Zevatskii, D.V. Samoilov, N.O. Mchedlov-Petrosyan, 2009, published in Zhurnal Obshchei Khimii, 2009, Vol. 79, No. 9, pp. 15041532.
Conthemporary Methods for the Experimental Determination of Dissociation Constants of Organic Acids in Solutions
Yu. E. Zevatskiia, D. V. Samoilova, and N. O. Mchedlov-Petrosyanb
a
St. Petersburg State Institute of Technology, Moskovskii pr. 26, St. Petersburg, 190013 Russia e-mail: yuri@newchem.ru b Karazin Kharkov National University, e-mail: mchedlov@univer.kharkov.ua
Received December 30, 2008
AbstractThe survey is dedicated to the critical analysis of different experimental methods of determining the dissociation constants (Ka) of organic acids in solutions. Advantages and disadvantages of the contemporary methods of rapid analysis used in biochemistry are considered. Special attention is paid to the problems of measurements in the nonaqueous media and to the reasons for possible incorrect results. The processes in solutions that should be taken into account for obtaining the correct values of dissociation constant are analyzed. On the basis of the consideration the recommendations directed toward an increase in the accuracy of measurements are given.
DOI: 10.1134/S1070363209090138 In concern with the fast development of pharmacology and adjacent fields of science (life science) for which the main method of study is highly effective bioscreening, special urgency acquires the task of determining the physicochemical parameters of bioactive compounds [1]. The physicochemical properties determining the complex of the basic pharmacodynamic and pharmacokinetic parameters of molecules (the so-called ADMET-l profile: absorption, distribution, metabolism, excretion, and toxicity) include the numerical characteristic of the acidbase properties of the molecules: pKa log Ka [24]. From the practical viewpoint it is of significance, that the pKa influences all transport properties of substances, i.e., possibility, direction and intensity of the processes of transfer, since this value determines the position of the acidbase equilibrium of a substance in the given medium, and hence the charge of equilibrium forms and the nature of electrostatic interactions [4]. At the same time, the value of pKa is the key characteristic of a substance used in physical organic chemistry. The analysis of changes in the pKa values makes possible quantitative estimation of the influence of two important factors, the structure of the substance and the nature of reaction medium [59], on the state of the chemical equilibrium. Dissociation Constants of Organic Acids in Solutions The thermodynamic value of the constant of acidic dissociation, Ka, characterizes the equilibrium of the proton transfer from the acid HA to the solvent molecule M with the formation of the lyonium ion and anion of the acid:
HA + M MH+ + A. (1)
For the simplification the solvated proton usually is designated by the symbol H+ and the scheme of equilibrium is written as:
HA H+ + A, (2)
although actually, by Brnsted, the matter concerns equilibrium (1) [5, 6]. The constant Ka is usually expressed through the activities of reactants in the reaction (1) in molar scale (3)
aA Ka = aH aHA . (3)
For the cationic acids that are considered as the product of the protonation of base B, the designation KBH+ is sometimes introduced, which actually is identical with Ka. An acid can be also anionic, dianionic, etc. Experimental methods usually allow c determination of the concentration values Ka of the
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ZEVATSKII et al. Scheme 1. HAMn + mM HA + (n + m)M H+ + A Hsolv + A + xM solv solv solv
constants, expressed through the equilibrium concentrations, or, still more frequently, the so-called mixed m constants Ka expressed through the lyonium ion activity and equilibrium concentrations of the remaining species.
c Ka
[A ] = [H ] [HA]
+
(4) (5)
m Ka
[A] = aH [HA]
In these cases, the thermodynamic value is calculated with the use of the concentration activity coefficients, for example:
Ka = aH [A] fA fA m = Ka . fHA [HA] fHA (6)
In studies of acidbase equilibria in solution, the pH scale plays the key role. In water, lower alcohols, DMSO (dimethyl sulfoxide), acetonitrile and some other solvents, as well as in many water-organic mixtures, this scale is determined sufficiently well. For the designation of the pH function in the nonaqueous solvents, the symbols of pHS [5] or pa* [7] are usually H used. As the standard state for the lyonium ion activity in a given solvent, a hypothetical solution of molarity (or molality) equal to unity, which possesses the properties of infinitely dilute solution, is taken. The simple scheme (1) of dissociation is not always realized. Thus, in the inert solvents of low polarity (benzene, toluene, hexane), the molecule of an acid is capable of release its proton only if a base is present in the solution; the transformation as a rule includes the step of the formation of the neutral H-bond complexes, and the acid anion remains in the form of an ion pair with the protonated base.
B + HA BHA BH+ A. (7)
In this case there are no free ions practically, and as a result the terms pHa and pKa lose sense. However, even in the solvents with the sufficiently high relative dielectric permeability r the scheme of the acid dissociation according to Izmailov [5, 8, 9] seems to be more complete. This scheme assumes that dissociates, strictly speaking, not an isolated acid HA, but the product of its solvation by the molecules of solvent M (Scheme 1). Furthermore, the association of lyonium ions with the solvated anions of acid into the ion pairs is possible. The latter are in equilibrium with the neutral molecules. It should be kept in mind that the electrochemical methods (potentiometry, conductometry) make it pos-
sible to estimate equilibrium constant between the free ions, on the one hand, and molecules and ion pairs, on the other [5], while spectrophotometric measurements can in certain cases give the ratio of equilibrium concentration [HA] and the sum [A ] + [H+ A ]. solv solv solv Although in the majority of cases of weak acids in polar solvents this difference between the dissociation and the ionization [6] is practically unnoticeable and these two terms are used as synonyms, nevertheless, it is always necessary to keep in mind that this can cause a difference in the values of pKa obtained by different methods. It is obvious from the aforesaid that the methods allowing to obtain the thermodynamic values of pKa are especially valuable. However, often the knowledge of the thermodynamic values of pKa is not necessary for solving the practical problems in biochemistry, chemical technology, etc., and this fact affects the trends in the development of the methods of experimental determination of pKa. In spite of the active development of the methods of theoretical calculation of pKa and the successes achieved recently in this the field [1012], the application and development of the methods of the experimental determination of pKa are continued, therewith the basic trend of development comprises the rapid methods [1326]. In principle, the values of pKa can be obtained from the analysis of dependence of any property of the compound under study on the index of the medium acidity. However, for the practical use of such dependence the following conditions should be met: (a) the selected property should be easily and reliably determined; (b) the obtained dependence should exclude other factors affecting the given property; (c) a singlevalued and desirably simple mathematical model connecting this dependence with the pKa value should exist. It is important that the acidity must be independently and reliably measured under the same conditions as this property. It is obvious that the conscious, forced, or disregarded nonobservance of these conditions being inherent in the chosen approach or another leads to regular decrease in the authenticity of the obtained results. From these positions we will evaluate the merits and deficiencies of the methods considered below.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 9 2009
CONTHEMPORARY METHODS FOR THE EXPERIMENTAL DETERMINATION
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In this survey we are restricted to the examination of the physicochemical principles, which determine possibilities and limitations for applying the basic approaches to the determination of pKa, and we leave after this framework the detailed consideration of the computational techniques, utilized for the obtaining the values of pKa from the experimental data in the complex cases. For this reason we do not consider here the special feature of the methods of determining pKa of the polybasic acids, which differ from those applied to the monobasic acids by a complex mathematical apparatus for experimental data processing. The increased interest since recently attract new approaches to the determination of the values of pKa, which we consider at first. New Approaches to the Determination of pKa Values In accordance with the above-considered tendency, in the last decade the rapid (express) procedures appeared, which combine the pKa determination with the separation of the mixture into the components. They include the various modes of high performance liquid chromatography (HPLC) [1318] and capillary electrophoresis (CE) [1926]. Interest in the application of separating methods is caused by the fact that for determining pKa, the isolation of the analyzed substance in the pure state and the measuring its concentration is not required, therewith, the quantity of substance can be small (several micrograms) [16]. Furthermore, in the biochemistry an important task is the determination of the acidbase properties of separate active centers (ionization microconstants), for which the best anything approach is the method of 13C or 15N NMR titration [2731]. This is connected with the fact that often the investigated mixtures of biologically active compounds are characterized by one pharmacological property. The physicochemical fundamentals of the determination of pKa by these methods in the classical version appeared as early as in the 80s of the twentieth century [3235]. Thus, use of HPLC for determining pKa is based on the registration of the dependence of the retention time of the confinement (or capacity factor) of the analyzed substance on pH with subsequent processing of obtained data on the basis of equation HardcastleJano [36] and the solvophobic theory [13]. The basis of the application of capillary electrophoresis for determining pKa is the registration of the analogous dependence of relative
mobility of cations or anions of the analyte on pH. The mathematical model, which connects the dependences with the value of pKa, is in this case analogous to that used for HPLC [16, 19]. Application of NMR for determining pKa [2731] is based on the registration of the dependence of the chemical shift of a nucleus (13C or 15N), nearest to the active center, on pH. The dependence of chemical shift on the ratio of the concentration of the protonated and nonprotonated forms of the analyte is linear, that is an advantage of this method [31]. Serious impulse to the development of NMR-based methods gave the application of twodimensional NMR [28, 30]. The method of capillary electrophoresis at the study of the acidbase properties in aqueous media is valuable because it allows direct measuring of pH at the capillary input and output [20], maintaining a constant value of ionic strenght and obtaining thermodynamic values of pKa [16, 17]. Since recently the CE was widely applied to determining pKa in nonaqueous media [2226], where these values differ significantly from those in water, as a result of the solvent effects, considered below. The application of CE is connected with the active use of organic solvents for increasing the separation efficiency. However, the authenticity of the results of pKa measurement was affected only negatively [22, 26], first of all due to the complexities of pH determination in the nonaqueous media [24, 25], which are in detail considered below. The use of additional external pressure accelerates the process of pKa determination, but decrease the separation efficiency [19, 20]. Liquid chromatography is used for the determining pKa in the form of reverse phase HPLC (RP HPLC) with constant pH of the eluent [13, 15, 16], or with the pH gradient depending lineary on the time [14, 15] with the application of hydrophobic viscous media as the stationary phase. The mostly used eluents are mixtures of water with methanol [16], acetonitrile [17], and other solvents [14]. It is obvious that the accuracy of the determination of pKa by gradient method is considerably lower, since the values of pH are obtained approximately from the empirical dependence [15]. The combination of separating methods with the contemporary high-speed methods of the registration of absorption and luminescence spectra with the use of photodiode matrices [15, 37] in the essence reduces them to the classical spectroscopic method, and it gives to them some of its advantages, which will be considered below.
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As follow from the comparative analysis of experimental data [14, 15, 19, 20, 3638] and as is correctly noted in [16, 20], the accuracy and authenticity of the values of pKa, obtained by traditional methods, nevertheless are considerably higher than with the use of a majority of the newly proposed approaches. Probably for this reason, in spite of the development of highspeed methods, the application of traditional ones is going on, both in combination with them [16, 17, 3942] and separately. In essence, mostly are applied the spectrophotometric method [4246] and the potentiometric titration [38 41, 4750], moreover, in the former the improved methods of registering electron absorption spectra are also used [38, 44, 46, 50, by 51]. Best productivity of the determination of pKa in water (4 min. for one measurement) is achieved with the use of a method of linear pH gradient [46], but the obtained pKa values differ on the average by 0.1 unit from those previously published when absorption spectrum is registered along the transparent tube in which pH depended lineary on the coordinate. The substantial part of the data on the dissociation of acids relates to the water [5263]. However, it is known that water levels differences in the acidic properties of the dissolved substances [5, 64]. From other side, equilibrium in the nonaqueous solvents [4, 6571] as a whole is of much more complex nature than in water. Therefore, let us consider in more detail the special features of different solvents. Classification of Solvents Determination of pKa values in various organic solvents and in particular elucidating the regularities in the influence of the medium on these values (solvent and medium effects) are significant both for physical organic chemistry and for solving practical problems [5, 72]. The difference in the pKa values in nonaqueous solvent and in water is expressed through the ws i indicies, the activity coefficients of the transfer from water into the given solvent [73] that is called also the activity coefficient of a solvent [74], the primary medium effect [7], the degenerate activity coefficient [7, 75] or the unified zero activity coefficients [5].
K K (in water) = log ws + log ws log wHs . H A A (8)
understanding of the equilibria characteristic for the selected solvent, and also incorrect construction of the pa* scale are the most frequent causes leading to H inadequate results at the determination of pKa. Let us consider from these positions the features of different groups of solvents. Most convenient is the classification of solvents based on their polarity (characterized by the dipole moment of molecules or by the relative dielectric permeability r) and the ability to be the donors of hydrogen bonds. It is accepted to distinguish by the last criterion, according to Bordwell, the solvents which are or are not the donors of hydrogen bonds [6, 76] (in abbreviated form DHB and NDHB respectively). The most common criteria of electrondonor and electronacceptor properties are Gutmans donor (DN) and acceptor (AN) numbers. The range of the pa* scale in a given H solvent is characterized by the index of autoprotolysis constant (pKS). The values of these parameters for some widely used solvents are presented in the table. The table includes also the values of the normalized Reichardts N polarity parameter ET and the index of the benzoic acid dissociation constant. There is a whole series of other parameters that characterize solvents; much valuable information about the nonaqueous solvents is given in new monographs [6, 71]. The nature of a change in pKa of acid upon transfer from one solvent to another is determined by a differrence in the values of r and of other properties of solvents, and also by the type of the charge of the studied acid and by the nature of the dissociating group [59]. As the standard solvent, water is taken most frequently. In this case the differentiating ones are called those solvents, upon transfer to which the difference in the strength of acids increase (the enhanced resolution of acid strength [77] is observed), and levelling are those solvents in which the aforementioned difference stays practically unaffected or strength of acids converges [5, 6, 64]. Equilibria in the Solvents with the Low and Medium Dielectric Permeability In the NDHB solvents of low polarity (r < 10) free ions are practically absent and therefore, as it has been indicated above, the pKa parameter should not be used. Such solvents include alkanes, haloalkanes, alkyl and halo derivatives of benzene, esters of carboxylic acid, ethers [tetrahydrofuran (THF), 1,4-dioxane]. The basic
The nature of prototropic processes in the nonaqueous media commonly differs significantly from that in water and in the aqueous mixtures with a significant content of water. Incorrect or incomplete
CONTHEMPORARY METHODS FOR THE EXPERIMENTAL DETERMINATION Parameters of some most widely used polar solvents a, b
Solvent Water Methanol Ethanol 2-Propanol 1-Butanol t-Butanol DMSO DMF Acetonitrile Acetone Propylene carbonate Nitromethane
a b
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, D c 1.85 1.70 1.69 1.66 1.66 1.66 4.05 3.81 3.90 2.88 4.94 3.60
r 78.4 32.7 24.6 18.319.2 17.4 12.5 46.4 36.7 35.9 20.6 64.9 35.9
DN 29.8 26.6 14.1 17.0 15.1 2.7
AN 54.8 41.4 37.5 33.6 32.2 27.1 19.3 16.0 18.9 12.5 18.3 20.5
N ET
pKS e 14.00 16.717.2 18.919.5 20.822.0 21.6 26.828.5 33.3 29.431.6 33.3 32.5 29 24
log ws H 0 +1.52 +1.94 3.40 2.52 +7.85 7 6.58.8
1.00 0.762 0.654 0.546 0.586 0.389d 0.444 0.386 0.460 0.355 0.472 0.481
The values of parameters commonly correspond to 25 and are selected by comparison of the published data [6, 68, 70, 71, 78, 79]. s The values of log wH for all solvents are found using the tetraphenylborate hypothesis [73] except for acetone [80]; for propylene s carbonate the estimation of log wH = 6.5 is obtained inderectly in [81]. c 1 D = 3.33561030 Q m. d at 30. e pKS is the constant of autoprotolysis
form of prototropic interaction in these media is the transfer of proton from the acid to the base, Eq. (7). Therefore comparative strength of acid in such solvents is evaluated either in terms of the constants of transmetallation (for the CH-acids) [8284], or with the use of the semineutralization potential of the acid with a base [85] and potential jump [86, 87], or in terms of complex formation [8889], and through the yield of the formation of ion pair with the bases of different force [9092]. These quantitative parameters of acidity depend not only on the properties of the studied acid in the solvent, but also on the strength of the appearing hydrogen-bonded ion pairs, but hence they depend on the selected base partner, and therefore are completely conditional [64, 93]. Therefore it was proposed to level the specific character of association in the ion pairs, using equilibria with the participation of the cations, whose charge was screened by macrocyclic ligand [94] or is strongly delocalized [95]. However, in such media also the formation is possible of more complex species: the dimers of ion pairs and larger aggregates [64, 72]. Furthermore, in the inert solvens of low polarity many acids can form dimers due to the intermolecular hydrogen bonds [64].
As to the low polar HBD solvents with the strongly expressed acidic or basic properties, they could solvate well the separate ions because of the ability to form hydrogen bonds, but the dissociation of ion pairs in such media can be insignificant because of the low dielectric constant. They include aliphatic carboxylic acids (besides formic), ethylenediamine, and others. The increased nonspecific ion association in alcohols becomes noticeable beginning with 1-butanol (r = 17.4), and it influences the nature of acidbase interactions complicating the determination of the pKa values [79, 96]. The same relates to t-butanol (r =12.5) [97, 98]. Equilibria in the Low Molecular Weight Alcohols and in Water The system of prototropic equilibria in the polar DHB solvents (methanol, ethanol, propanol-1, ethylene glycol) is similar to the same in the water. These alcohols and water are good donors and acceptors of hydrogen bonds. They well solvate anions and cations, although their r values are less than that of water. The scales of pa* in these solvents were determined H reliably enough (pKS = 1722) and the experimental methods of measuring the pKa also are practically the
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same as in water, since the ionic association in these media is weakly expressed. By the effect on the pKa value they belong to the leveling solvents. But even in water, whose set of pKa values was obtained before 5060-ies of the XX century [5257], both the scale of pH and the methods of measuring this value were finally established in the 80-ies in the form of the recommendations of IUPAC [99], there were problems with the experimental determination of pKa. Firstly, the measurements must be carried out at a sufficiently low ionic strenght (desirably at 0.01 mol l1) and corrections should be made accounting for the ionic strenght according to the equations of Debye c m Hueckel or Davis for conversion of the Ka and Ka values to the thermodynamic values Ka. For determining pKa of the sufficiently strong (< 2) and very weak (>11) acids solutions may be required with pa* < 1 and pa* > 12, where the ionic strenght is H H out of the region of the applicability of the mentioned equations. Furthermore, in this field the use of glass electrode is hindered by acidic and alkaline errors (see further). Therefore the values of pa* in these media H usually are not measured, but they are created by strong acids and bases. In this case the Hammett functions of acidity are used for the acid and alkaline regions. The majority of acidity functions (H0, H''', HR, H, etc.) were measured in the aqueous solutions of mineral and some organic acids already by 1983 [100]. In the survey indicated are compiled more than 400 different functions of acidity, including those for the highly basic media (H and others), for water-organic and nonaqueous solvents; there are references to the most important generalizing publications on acidity functions. Additional information on the functions of acidity can be found in [101, 102]. An essential practical problem in the determination of pKa in water is a low solubility in it of many organic compounds. For the substances with the large molecules (dyes, the fragments of biomolecules, etc.) that are sufficiently well solnble in the water, the formation of dimers and even more complex aggregates due to hydrophobic and van der Waals interactions frequently is observed. This leads to the distortion of the interaction stoichiometry, of the absorption spectra and as a consequence to inadequate results [103].
Equilibria in the Polar NDHB Solvents Much more interesting from the theoretical point of view but more complex from the practical side is the initiated in the middle of 20th century and continued up to now study of prototropic equilibria in the dipolar proton-free, or the NDHB solvents that are characterized by a comparatively high value of r (> 20) and by the absence of OH groups. In these solvents the majority of organic compounds is readily soluble, small anions (OH, F) are spairingly solvated, and large anions with the delocalized charge like iodide, iodine-iodide, picrates, tetraphenylborate, etc., are well solvated [6]. For these solvents the scale of pa* is sufficiently H extended (pKS usually up to 30 units and more), they possess a clearly expressed differentiating action. The extension of the acidity scale leads to a sharp increase in the influence of any structural differences on the relative strength of the dissolved acid. Furthermore, the incapability of the solvent to behave as a hydrogen bond donor leads to the destabilization, first of all, of the anions with the localized charge. The solvents of this extensive class are subdivided in their turn in two large groups: protophobic and protophilic. The first ones include, in particular, acetonitrile, benzonitrile, nitromethane, nitrobenzene, propylene carbonate, sulfolane, and also not too polar ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone). These solvents weakly solvate proton and other cations, they are characterized by low DN values s and by positive values of lg wH, and nitrobenzene and especially nitromethane can in some cases even manifest acidic properties [104]. In these solvents sharply increases the strength of a base [105, 106]. The typical representatives of protophilic NDHB solvents are, in particular, DMF (dimethylformamide), N,N-dimethylacetamide, DMSO (dimethyl sulfoxide), and HMPA (hexamethylphosphoramide). They are of sufficiently high basicity, solvate well cations, first of all the cations of metals, and also other Lewis acids, s are characterized by negative values of log wH and by high DN values. If in the acetonitrile the values of the pKa of carboxylic acid and phenols are extended almost over the entire scale of pa* (the pKa of benzoic acid H becomes equal to 20.7 [107]), then in DMSO (dimethyl sulfoxide) they, in spite of specific increase, remain within the limits of the first half of the acidity scale (pKa of benzoic acid in DMSO equals 11.1 [81]).
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But CH-acids are strengthened noticeably, since the combination of high basicity and polarity in the molecules of aprotic DMSO stabilizes carbanions [67, 108112]. The summary of the pKa values of acids in the polar NDHB solvents is collected in the book by Izutsu [68]. Association of Ions. Homo- and Heteroassociation At the determination of the pK values, the complications connected with the nonspecific (Coulomb) cationanion association (C+ + A C+A) can be manifested in the solvents of any nature when r value is less than 20 units. The precise limit of r is difficult to determine, since here not only the nature of ions and solvent is significant, but also the concentration of electrolytes and the temperature. When the concentrations corresponds to those usually used in the experiment, at the value of association constant Kass above 103 l mol1, this process is not neglegible [74]. In this case at the potentiometric studies the equilibrium concentration [A] necessary for the calculation of pKa on the basis of the value of pa* of H the buffer mixture (HA + CA) should be calculated proceeding from the value of Kass. The Kass constants most frequently are determined conductometrically [113], sometimes potentiometrically [114] or spectrophotometrically [115118]. But ionic association can also occur in the polar NDHB solvents with comparatively high values of r. In these media the ion pairs with the strong specific interaction are stable, for example:
BH+ + A BH+..A. (9)
This phenomenon is caused by the insufficient hydrogen bonding and by the poor solvation of anions. As a result the hydrogen bonds between ions and molecules of acid are more durable than between the molecules of acid and the solvent. In accordance with the recommendations of IUPAC this is called homoassociation [120]. A systematic study of this phenomenon began in 1961 [121]. Such processes are observed even in water solutions (for benzoic and hydrofluoric acid [58, 59]). But they are especially characteristic for the NDHB solvents. If a solution contains different acids, then the socalled heteroassociation is possible, i.e., the formation of the mixed complexes of the type of AHX and XHA [77, 122124]. Analogous interactions can occur between the base and the cation formed at its protonation, moreover, both of cations, BH+ and BH+B, can associate with the anions [125]
BH+ + B BH+B, the constant is K f +, HA (11)
but as a whole cations in the NDHB solvents are solvated better than anions, and the values of the corresponding formation constants (Kf) in this case are smaller. The solvents with the clearly expressed protophobic properties, for example, nitromethane comprise an exception [126128]. Both homo- and heteroassociation is especially strongly expressed in the protophobic solvents: nitromethane, nitrobenzene, acetonitrile, benzonitrile, propylene carbonate, acetone, methyl isobutyl ketone [122, 105, 129136]; it is somewhat weaker in DMF (dimethylformamide) [136], still weaker in DMSO (dimethyl sulfoxide) [77, 81]. Naturally, protophilic solvents (acceptors of hydrogen bond) compete with the anions of acid Afor the molecules HA.
The values of the formation constants of HA2 5 1 complexes can reach the order of magnitude 10 l mol [77, 132, 137139]. They usually are determined by the potentiometric measurements [77, 123, 134, 139], by the method of solubility [122, 140], conductometry [of 81, 141], and sometimes spectrophotometry [120, 134, 142], and since recently also by capillary electrophoresis [24, 26, 124, 143].
In particular, similar effect provokes the difference in the association of quaternary alkylammonium ions and the cations containing NH group with the anions weakly solvated in acetone, methyl ethyl ketone, and acetonitrile, that is manifested in the revealed already by Walden [5, 6] differentiating action toward dissociation of salts. The negative influence of the association of anions with the cations of metals can be considerably decreased by introduction into the studied solution of cryptands and crown ethers binding the cations of metals [119]. The strongly expressed formation of the associates between the acid and its anion is another special feature of polar NDHB solvents
A + HA AHA, the constant is K f . HA (10)
Of course, the associates where the anion is connected with the cation by a hydrogen bond are especially stable: A+HB.
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In a number of cases the phenomena observed in the solvents originate from the formation of species with a more complex stoichiometry [135, 142, 144, 145]
A + n HA
content should be monitored [150]. These peroxides exhibt acidic properties [93]. Nitromethane, in view of its expressed CH-acidity, can serve as a proton donor in the presence of such bases as Cl and Br, contributing to the formation of the particles HCl2 and HBr2, and also can provide esters [104, 151]. Special procedures for the purification of methanol, ethanol, DMSO, formamide, acetonitrile, THF, dioxane are given in the recommendations of IUPAC [152156], and for the remaining solvents, in the special reference books [149, 150]. Hydrogen chloride is often used for standardizing cells with liquid junction and without liquid function both in water and in nonaqueous solutions [7, 157]. But information exists on the insufficient stability of the HCl solutions in formamide [158], and at the saturation of acetone with gaseous HCl the formation of phorone and mesityl oxide is possible. It is possible at the creation of the high values of pa* and also at the titration of acids in alcohols to use H alkali metal hydroxides or, better still, alkoxides. In the NDHB solvents the alkalis are spairingly soluble; adding crown-ethers or cryptands makes it possible to increase substantially the solubility of alkalis [159]. Alkalis and other strong bases can cause the aldol condensation of acetone. Hydroxides of tetraalkylammonium are often used [95, 160163]. Alkoxylates of metals in DMSO can be converted into the dimsyl ion CH3SOCH2 [164], and very strong bases can initiate oligomerization of acetonitrile [165]. With the NDHB solvents it is convenient to use amines as bases, but the products of their protonation can specifically interact with the anions due to the Hbonding. At measuring pKa in acetone it should be taken into account that it can react with the primary amines to form Schiff base even at room temperature [162, 166, 167]. Other bases used with the NDHB solvents are 1,8bis(dimethylamino)naphthalene (the proton sponge), 1,2-diazabicyclo[2.2.2]octane [168], as well as the superbase 1,8-diazabicyclo[5.4.0]-7-undecene (DBU). As the components of buffer mixtures for organic solvents it is convenient to use tetraalkylammonium salts with nitrophenols. Tetraalkylammonum salt of carboxylic acid not always can be successfully obtained in a sufficiently pure form and in the consistency convenient for application [141, 169].
(HA)nA .
(12)
If the results of potentiometric or spectrophotometric measurements are processed without taking into account this phenomenon, then apparent values of pKa are obtained, which strongly differ from the thermodynamic ones. The method of the accounting for the homoassociation in the calculation of the pKa noticeably influences the results. Therefore presumeably the value of the pKa of benzoic acid in the nitromethane, according to the data of different research groups, are different: 13.2 [146], 15.0 [147], 17.7 [70] and 19.5 [138]. The complexity of equilibrium analysis with accounting for homoassociation superimposed on usual acid dissociation, is clearly illustrated by the fact that in a series of the publications of Kolthoff with the colleagues [121, 129] the Kf and pKa values of HA picric acid in the acetonitrile have been repeatedly reconsidered, until final values have been obtained (0.3 and 11.0, respectively). The Chemical Features of Solvents. Reactions with Strong Acids and Bases At the experimental determination of pKa in the organic solvents it should be taken in the consideration that the solvent is not always an inert medium and can enter into reactions with the studied substance, the components of buffer mixture and can undergo autoreactions under the action of admixtures, air or light. Great problems appear with the formation in the course of these reactions of the admixtures of acidic or basic nature, and also due to the presence of water. It is necessary also to keep in mind that organic solvents dissolve oxygen and carbon dioxide much better than water. It is desirable to work in the inert atmosphere (dry nitrogen, argon). Pure DMF (dimethylformamide) and acetonitrile in the presence of the traces of moisture are gradually decomposed with the formation of dimethyl- and methylamines [148, 136]. Pure formamide is also unstable even in a nitrogen atmosphere [149]. In the highly acidic and highly alkaline medium many decomposition reactions (for example, of 1,4-dioxane) are accelerated. Furthermore, for dioxane and THF the formation of peroxides is very characteristic, whose
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A significant problem at measuring pKa in the nonaqueous media creates the water impurity [170], and most solvents are very hygroscopic. At the presence even of trace quantities of water (less than 0.01 wt %) in a protophobic solvent which is less basic than water (acetonitrile, acetone, propylene carbonate, nitromethane, nitrobenzene, sulfolane) the ions of hydronium are formed instead of the lyonium. This leads to sharp reduction in the observed value of pKa. For example, the content in acetone of 0.01 mol l1 of H2O reduces the value of pKa of picric acid by 2 logarithmic units [171]. In alcohols and especially in the protophilic solvents (DMSO, DMF) the admixture of water does not just radically influence the prototropic equilibria. But if in DMSO or DMF the acids weaker than water are studied, the admixture of water distorts the results strongly. It was shown recently that the addition of 15 mol % of protophilic solvent (DMSO) to the the protophobic one (acetone) sharply decreases the sensitivity of the pKa value to the presence of water [171]. This is caused by the fact that DMSO is considerably more basic than water, and even in water presence in the system the lyonium ion is formed of composition + H(DMSO)2 , but not a hydrated proton. Therefore the values of pKa in such system are considerably lower than in pure acetone. The perchloric acid is added to organic solvents in the form of concentrated aqueous solution, and for water binding acetic anhydride is used [105]. Thermodynamic Values of pKa and Activity Coefficients Since any experimental determination of the pKa value in solutions is performed in the presence of ions at a certain value of the ionic strenght I, it is necessary for obtaining the thermodynamic values of pKa by any manner to estimate the ionic entration activity coefficients [see, for example, Eq. (5)]. Most often the study is carried out at the low I value, assuming the activity coefficients of molecules equal to unity, and the values of ionic activity coefficients are calculated from DebyeHueckel equation. For the activity coefficient of ith ion with the charge zi in dilute solutions the second approximation of DebyeHueckel takes the form
Azi2 I
where A and B are the coefficients depending on the values of r and temperature, a is the so-called ionic parameter which characterizes the average distance of the approchement of the solvated ions. In the aqueous solution at 25C in the molar scale A = 0.510, B = 0.3291010 m1; the first approximation of Debye Hueckel (log fi = Azi2 I) is applicable at I 0.01 mol l1 [74]. Equation (13) is applicable, probably, at I 0.1 mol l1 [7]. The same expressions usually are applied also to the calculation of fi values in the nonaqueous media. But the lower the value of r, the lower the value of the I that allows application of these equations. Furthermore, the values of the parameters B and, especially, A become higher, and the uncertainty introduced into the value of pKa by correction for activity coefficients grows. Thus, the value of A is 1.12 in DMSO and 8.02 in tert-butanol. Therefore in the nonaqueous media with the r values lower than that of water, the value of ionic activity coefficients already at the very small ionic strenght considerably differs from unit. Furthermore, under the conditions of the incomplete dissociation of salts for evaluating the equilibrium I value it is necessary to apply iterative procedure: successive refinement of fi value and of equilibrium composition of the system. The estimations of the value of the parameter a according to the data of different studies usually vary in the range 0.30.5 nm [7]; for the ions of sulfophthaleins and benzoines it was suggested to assume a = 0.7 nm [172]. According to the condition of BatesGuggenheim, Ba = 1.5 [7] which corresponds to a = 0.456 nm. The same value is used also in the nonaqueous media [173176]. In other works for evaluating the thermodynamic values in the water mixtures and the nonaqueous solutions the dependence
m of K on ( I )/(1 + I ) was used [177].
log fi =
, 1 + Ba I
(13)
For evaluating the thermodynamic constants in the aqueous solutions often were used other equations, which make it possible to enlarge the field of application of the DebyeHckel equation by adding to the right side of a term proportional to I, for example, Davies and StokesRobinson equations, etc. [7, 52, 157, 178-180]. In this case, one should consider that with the high I values the activity coefficients of molecules already can noticeably differ from unity and must be determined in the independent experiments, for example by the methods of solubility or partition [59].
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ZEVATSKII et al.
m For describing the dependence of the values of K of many organic acids from I in aqueous solutions in a wide range of the concentrations of various supporting electrolytes polynomials were proposed whose absolute terms can be regarded as the desired values of m pKa [59]. For the aqueous solutions only the K or c pK values at the fixed high ionic strenght (I > 0.1 mol l1) [56, 59] are come times used but in this case the obtained constants correspond only to this ionic strenght; a significant role plays the individuality of supporting electrolyte. At the potentiometric study of acidbase equilibria in the nonaqueous solutions attempts were also made to level the effect of inconstancy of I by introduction of a supporting electrolyte [97, 181]. But because of the probable ionic association the experimentally determ mined constant is the combination of K and Kass. More common method consists in the extrapolation of the dependence of the index of the concentration or mixed constant on the concentration of electrolyte to I 0. From the point of view of the authenticity of the obtained pKa values potentiometric, conductometric and spectrophotometric method proved to be the best. Furthermore, they provide great opportunities for the careful study of the influence of the solvent and of medium acidity on the complex of the acidbase equilibria in the solutions. Therefore we consider these methods in greater detail. Since potentiometry appears to be the basic method of pH (pa* ) measurement that H in the general case is indispensable for the determination of pKa, then the consideration should be started precisely with this method.
where the salts are dissociated completely and the equilibrium concentration of cation, [C+] is much higher than [H+] the following equation is valid for the c concentration pK value at the initial concentrations of acid and salt cHA and cCA respectively:
c pKa =
cHA[Cl] (E E0)F . + log 2.303RT cCA
(15)
Here E is the electromotive force (emf) of the chain at the given concentrations, E0 is the standard emf value of the chain, F is the Faraday number, R is the gas constant, T is the absolute temperature. When possible, E0 value is determined initially (for example, in dilute solutions of hydrogen chloride) [52, c 182], the values of pK are calculated, and then they are extrapolated to the zero ionic strenght [183] or by any method ionic activity coefficients are calculated. In the cells without liquid junction it is possible to use also simpler for use glass [114, 157] or quinhydrone [184186] electrodes. But in this case all those problems appear, which are characteristic of these indicator (sensory) electrodes. These problems will be considerd below. Recently more often the reversible toward the hydrogen ions glass electrodes are used in the cell with liquid junction. For example, in the work with the aqueous solutions [59, 157] the chain was often used
Glass electrode | HA, CA || KCl (satur.) | AgCl, Ag. (16)
Potentiometric Method It is believed that the most reliable values of pKa are determined in the cells without liquid junction (error 0.005 and below); the values, found with the error of 0.04 are regarded as approximate, and with the error over 0.04, inaccurate [59]. But this concerns first of all the aqueous solutions; in the organic solvents, as a result of the smaller certainty of the scale of pa* and, as a rule, of the larger corrections on the H concentration activity coefficients, even the error of 0.1 in some cases is acceptable. The most correct and accurate results are obtained with the hydrogen electrode in chain (14) [182].
Pt (H2) | HA, CA, NaCl | AgCl, Ag. (14)
Instead of the the silver chloride electrode the saturated calomel elrctrode, KCl(sat), Hg2Cl2, Hg, is used. For the nonaqueous media often other connecting solutions of electrolytes are applied, which will be considered below. Two basic procedures are possible: pH-metric titration and the method of the separate fillings [187]. In all cases in the working solution arises a buffer mixture, and the value of the index of the mixed dissociation constant is calculated from the equation:
m * pKa = paH log
[A] [HA]
(17)
Sometimes as reference electrode the calomel electrode (Hg2Cl2, Hg) is used. For water or solvent
Analogous relationships exist for the equilibrium of base B and combined cation HB+, if the working cell contains a mixture of base and its salt or if the base B is titrated with acid. In the case of titration the calculation of dilutions due to the addition of the titrant is necessary, and at the calculation of equilibrium
1869
concentrations in the case of the acids of moderate strength it is necessary to consider the value of [H+] in the material balance and the equation of electroneutrality; in this case the calculation formulas get somewhat complicated [59, 188]. Direct determination of relative constants, Kr [66], by measurement in the concentration chains [181, 189, 190], is possible in principle either with the hydrogen or quinhydrone electrodes, or with the glass electrode, but too high electrical resistance of the latter is an interfering factor. Measurement of emf of a cell with liquid function (18) allows the estimation of the ratio of the dissociation constants of the examined acid HA and the acid HA0 taken as a reference:
Pt (H2) | HA, CA || HA0, CA0 | (H2) Pt. (18)
In this case reliable results are obtained quite simply under the conditions for the complete dissociation of salts and the absence of homoassociation. The correct choice of working concentrations is of especial significance [187]. The initial concentrations within the range 0.010.001 mol/l usually are used, but the concentrations of titrant can be higher during the titration, if its solution is added by small portions. From the point of view of accuracy, the region of the half-neutralization of the acid is optimum, but usually the range 2575% of neutralization is used [191], since it is desirable to be convinced in the constancy of the determined pKa value and, thus, in the adequacy of the assumed scheme of ionic equilibria. The diverse variants of the titration are possible, for example, titration of the solution of acid HA with alkali either of the solution of salt NaA with hydrogen chloride or perchloric acid. As far as it is possible, it is desirable to maintain the constant ionic strenght by adding background electrolyte both to the titrated and titrant solution. It is possible to use the method of successive dilutions in the measuring cell by the solvent containing the same salt [97]. Potentiometry is the convenient method of determining pKa, if the calibration of measuring system makes it possible to obtain the reliable values of pa* of the H working solutions [of 71, 129]. To the merits of the potentiometric method can be attributed the ease of the automation of the titration. Good results were obtained by the titration of aliphatic and aromatic carboxylic acid in the mixtures of water with methanol, ethanol, 2-propanol, 1,4-dioxane, DMSO and DMF, with the use of a glass electrode in the cell with liquid junction [177].
In the cells with liquid junction, the value of Eo is no longer the same strictly constant as in the cells without liquid junction, and it must be determined regularly in the course of calibration against the reference solutions (see below). It was reported that the E0 value can somewhat change after removing of glass electrode from the solution, therefore special methods of work are proposed [187, 192, 193]. Titration makes it possible to comparatively easily determine many values of pa* , but in this case it is H necessary to check the attaining of electrode equilibrium after each adding of the titrant solution, and also to be confident that any drift of E0 and of electrode hydrogen function is absent. As a whole, in the nonaqueous media the potential of glass electrode is attained much slower than in water, and at rapid addition of titrant the recorded values of potential can differ significantly from the the equilibrium values [71], which leads to the erroneous values of pa* and hence of pKa. Therefore the method H of separate infills can prove to be more preferably [194, 195]. The potentiometric determination of pKa in organic solvents can be complicated by the incomplete dissociation of salts and by homoassociation. In the case of the incomplete dissociation of the salt formed by the examined acids, the potentiometric method can give only the combination of constants Ka and Kass. Thus, it is shown that during the estimation of the value of pKa according to the data on the emf of cells without liquid junction in water1,4-dioxane mixture (r = 19.07) the accounting for the incomplete dissociation of sodium acetate is necessary [114]. For determining the real values of pKa in tertbutanol, where the values of the constants of cation anionic association for different salts, perchloric and picric acids, and for tetra-n-butylammonium salts of aliphatic acids and phenols fell to the range from 104 to 2105, a combination of potentiometric and conductometric measurements was used [97, 98]. The association of anion A with metal cation can be reduced by binding the latter into the complexes with a macrocyclic ligands, for example, with a crown ether or a cryptand [119, 159]. In polar NDHB solvents, especially in protophobic ones, the interfering influence of homoassociation gets the most important. Let us consider the effect of homoassociation on the nature of the dependence of pa* of buffer mixture H
1870 4 3 pH pKa log f1 2 1 0 1 2 3 4 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 e d c
ZEVATSKII et al.
dissociation constant of acid, and then, using this value, to find the value of Kf from the whole depenHA dence of pa* on the composition of buffer mixture. H
b a
Thus, the measurement of pa* of the solutions of H acids at 50% of neutralization makes it possible to estimate the value of pKa even under the conditions of homoassociation. The pKa values of 38 monosubstituted benzoic acids in the semineutralization point were estimated by this procedure [78] not only in methanol and ethanol, but also in DMF, acetonitrile, sulfolane and, acetone. But therewith it should be taken into account that at the Kf > 100 the buffer capacity at the ratio HA ca/cS = 1: 1 is no longer maximum as in the simple scheme of acid dissociation, but is close to the minimum [71, 129]. Even more complex is the case when in the buffer mixtures besides the homoassociation is possible also the unspecific cationanion association, as it takes place in methyl isobutyl ketone [130] or in acetone [135]. Then the calculations are noticeably complicated, since the calculation of several parameters at once is necessary, even when the value of the dissociation constant of the buffer salt is known or it is preliminarily determined from conductometric data. Electrodes for the Potentiometry For obtaining the adequate values of pKa it is important also to consider special features and limitations of the electrodes used for measuring the instrumental values of pH. The primary standard for the potentiometric measurements is the hydrogen electrode, and it was used in the fundamental research of the USA National Bureau of Standards (NBS, now NIST) on the measurement of pH [7, 75, 194, 195]. The electrode consists of a platinum plate (usually covered with activated platinum) submerged into the measured solution, through which hydrogen is passed. If the electrode is in exact working state, the potential of the metering circuit involving the hydrogen electrode and the reference electrode [Eq. (20)] strictly obeys the Nernst's equation, and the slope of the hydrogen function is always theoretical. The hydrogen electrode makes it possible to determine the values of pH of aqueous solutions up to 1214 which is problematic with the use of a glass electrode. However, it is inconvenient for the operation, in particular, because
0.9
ca/(ca + cs)
Plots of reduced pa* pKa log f1 values against the ratio H ca/(ca + cs) 100% at various values of Kf(HA): (a) 0, 2 (b)10, (c) 102, (d) 103, and (e) 104.
(HA + CA) on the ratio of concentrations of acid (c) and its salt (cs) in the case when CA dissociates completely. The last condition is usually satisfied sufficiently strictly in the case, when r > 20, and as C+ is used the cation of tetraalkylammonium or tetraphenylarsonium. The homoassociation specifically distorts the expected curve of the potentiometric titration. Thus, when [C+] >> [H+] and n = 1 the dependence of pa* on H the initial (analytical) concentrations c and cs is described by the equation:
2 a* 2f12cs a* 2f1Ka[ca + cs + K fHA(ca cs)2] + Ka ca = 0, (19) H H
where f1 is activity coefficient of a single-charged ion. The value of the pKa and the constant of homoassociation can be found numerically. For the optimum values of K and Kf the dependence of pa* on HA H ca/(ca + cs) calculated by Eq. (19) best coincides with the experimental titration curve [129]. The distortion of the curves of the potentiometric titration makes it possible to reveal the presence of homoassociation [133135]. In the case of pronounced homoassociation the ions A practically do not occur in the solution, and prevails the equilibrium 2HA H+ + HA2 . The homoassociation is seen from the deviation from linearity of the plot of pa* of buffer solutions against H the logarithm of the ratio of concentrations of the buffer acid and its salt. In this case, it follows from Eq. (19) that if ca = cS, then the relationship: K = pa* log f1 is correct. By H this route is possible to determine the value of the
1871
of easy poisoning and the interaction with the studied substances and the organic solvents [7].
Pt(H2) | H+, Cl | AgCl, Ag. (20)
The reproducible results with the hydrogen electrode were obtained in pure alcohols [7, 157], in ethanol with the addition of toluene [196], in water ethanol mixtures [197], in formamide [158, 185, 198], propylene carbonate [199], in acetone [200] and wateracetone system [201]. In the last system, according to the data of some authors, more preferable is found to be the non-platinated platinum electrode, or an electrode, covered with palladium. In the literature, important details of work with the hydrogen electrode have been published [6, 7, 202]. Together with a study of standard cell, the values E0 of the cells with silver bromide and silver iodide electrodes are determined in the nonaqueous media [203]. Alongside the hydrogen electrode, the quinhydrone electrode is used for a long time, consisting of a platinum wire, sometimes with the golden plate [6, 7, 181], placed into the solution of quinhydrone, the molecular compound of quinone and hydroquinone(1,4-dihydroxybenzene). The sensitivity of quinhydrone electrode to pH is determined by the reversible reaction: Q + 2e + 2H+ H2Q. Therefore in water the electrode cannot work at pH > 8, since under the conditions of hydroquinone deprotonation the redox process proceeds without the participation of proton. The quinhydrone electrode can serve as a good alternative to the glass electrode at the work in the region of low pH. Although this electrode sometimes is used in the cells without liquid junction [184186, 204], more frequently it applied to the cells with liquid junction [of 181, 189, 190, 205], since both benzoquinone and hydroquinone are quite reactive compounds. At present the glass electrode is used most widely as a measuring electrode. It is a silver wire, dipped in the solution of hydrochloric acid in the sealed glass ampule. The lower part of the ampule is a gkass membrane with a gel permeable for protons on its surface; the electrode is immersed in the measured solution [5, 7]. In water in the range of pH from 2 to 12 the dependence of efm of the metering circuit with reference electrode on pH (the hydrogen function of the electrode) is linear with the slope k close to the theoretical one. In detail the theory and the operating principle of glass electrode are treated in the works of Nikolskii and coauthors [206, 207].
At very high (>12) or very low (<2) values of pH in water deviations are observed from the linearity of the hydrogen function (alkaline and acidic errors, respectively) [208]. IUPAC recommends a method [209] allowing quantitative estimation of alkaline error at the alkali concentration up to 1 mol l1 and decreasing errors when working in these regions. Empirical dependences are used since recently that account for the nonlinearities introduced into the hydrogen function by different factors [39, 44, 210, 211]. As said above, according to some data the main disadvantage of the glass electrode at the measurements in the nonaqueous media in the chain with the liquid function is the fact that the equilibrium potential can be achieved extremely slowly (up to several hours) [71, 212]. Furthermore, hydrogen function in the nonaqueous media is frequently distorted, and it must be thoroughly accounted for even when this electrode ideally behaves in the aqueous solutions. An extensive information on the use of a glass electrode in the water-organic and nonaqueous media is accumulated to the moment. Thus, glass electrode responses to the acidity change in the mixtures of water with methanol [173, 174, 213215] and ethanol [197], in methanol [70], ethanol [7, 191] and its mixture with toluene [196], in the mixtures of methanol and ethanol with benzene, in the methanol-benzene-water and ethanol-benzenewater mixtures [157], in butanol-1 [216], propanol-2 [217221] and the mixtures of propanol-2 with 1,4dioxane [157], in t-butanol [97, 98, 217, 219, 222], ethylene glycol [216], formamide [70], in DMSO [70, 81, 159, 216, 223], DMF [70, 136, 145, 160, 183, 224], acetone [70, 106, 135, 167, 225227], in methyl isobutyl ketone [130, 160], acetonitrile [70, 77, 122, 140, 228, 229], benzonitrile [70, 139], sulfolane [144], propylene carbonate [70, 137, 199, 230], nitromethane [70, 126128, 231], and nitrobenzene [160, 175]. The extensive studies of acid-base equilibrium with the use of a glass electrode in different water mixtures conducted Douheret [194, 195] and Alexandrov with co-workers [157]. The functioning of glass electrode in the nonaqueous medium substantially depends on the type of glass [7, 157]. The technology of the preparation of glass electrode for the work has been described [7, 135]. There is a set of other electrodes that can be used in the nonaqueous media as the indicator electrodes [7, 232]. Izutsu et al. examined a series of electrodes
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sensitive to pH on the basis of semiconductors (IrO2, Si3N4, Ta2O5) for measuring pH in anhydrous solvents. The electrodes were found to exceed by an order of magnitude the glass electrode with respect to the time of achieving the equilibrium potential [71, 212]. A valuable information on the application of indicator electrodes and reference electrodes in the nonaqueous media and on the procedure of performing the titration is collected in a number of surveys [162, 233]. As to the reference electrodes, the main requirement for them is the retention of a constant potential in a given medium [176]. At the work in the nonaqueous solvents in the cells without transference, the dissolution of silver chloride is possible due to the formation of complex anions not only in DMSO and acetone [157, 200], but also in aqueous ethanol [234, 235]
AgCl + n Cl [AgCln+1]n. (21)
(Furthermore, the presence of amines in the solution also leads to the dissolution of AgCl.) The processes analogous to Eq. (21) are possible at the use of a calomel electrode [176], but it is less subjected to this effect [71, 236]. More reliable is the use of a tallium bromide electrode [186]. At present the determinations of pKa are carried out mostly using the cells with liquid junction. In this case together with the silver chloride and calomel electrodes are used another reference electrodes, for example, silver in the dilute solution of silver nitrate in the organic solvent [106, 130, 140, 136, 197, 217, 224]. At the work with nonaqueous solutions in the cells with liquid junction both with silver chloride and with calomel electrodes the saturated solution of KCl in the water usually is replaced by solutions (often saturated) of tetraalkylammonium chlorides or other salts in the studied or in another organic solvent [128, 145, 175, 176, 227, 230, 232, 237]. Furthermore, special reference electrodes were developed for the measurement in the nonaqueous media (silverionic, silverioniccryptate, platinum iodine) [71], but they did not find wide application. Obviously, this is defined by other reasons than the high price and the small volume of production. For obtaining reproducible and correct results the selection of liquid compound plays an important role. The comparison of emf measurements in the cells with liquid junction in 50 wt % aqueous methanol solutions
containing buffer mixtures showed that the use of the connecting bridge filled with the investigated solvent was preferable [174]. For preventing various undesirable processes including the influence of the lyonium ions or hydroxy ions on the diffusion potential, a dual electrolytic bridge is sometimes used [123, 224, 229]. At the analysis of equilibria in NDHB solvents the bridges were filled mostly with the solutions of perchlorates and other tetraalkylammonium salts in the solvent under study [123, 128, 130, 135, 175, 199, 224, 225, 227, 238]. At the study of the alcohol solutions in the cells with liquid junction the saturated KCl solution is used [220] or 10-fold diluted saturated solution of LiCl [191] in the same alcohol. In the case of t-butanol the bridge was filled with the solution of potassium chloride in the mixture of this solvent with water [223]. Sometimes the methanol solutions of potassium or tetraethylammonium chlorides are used in the bridges also in the study of other solvents [69, 220]. The constructions of connecting bridges are diverse and have been described in detail [7, 157]. Finally, the question on the standardization of the acidity scale plays the key role (see further). Let us mention the two additional thermodynamic methods of the pKa determination that include invariably the determination of pH values: the methods of solubility and of partition [236]. For example, for a poorly soluble in water acid HA the dependence of solubility Si on the pH of aqueous phase in a series of buffer solutions with a constant ionic strenght is expressed by the equation
log
m where S0 is the proper solubility of HA molecules, Ka is the mixed dissociation constant of the acid at the given ionic strength [Eq. (4)]. The value of S0 usually is determined under the conditions of the complete absence of A ions in the solution above the bottom phase. It is important also to be sure in reaching the heterogeneous equilibrium which usually is monitored by the change in the solubility in time and the agreement is cheked of its value obtained at a given temperature both in the course of cooling and heating. It is necessary also to keep in mind that too vigorous stirring of the system can lead to the formation of colloid solutions. In the solutions with very low ionic strenght it is possible to estimate the thermodynamic value of pKa, by assuming fHA = 1 and by calculating fA by the DebyeHueckel equation. At the high ionic
Si S0 m = pH pKa , S0
(22)
1873
strenght the S0 dependence on I is used for determining fHA [59]. In the organic solvents the solubility of organic acids usually is too high for determining pKa, but an increase in the solubility of the salt CA owing to the effect of the additive of acid HA makes it possible to reveal the formation of HA2 species in the solvent [140]. In the method of partition analogously the dependence is used of the partition factor of an acid or a base between the water and a solvent practically immiscible with water. If the solvent is low polar, for example, benzene, toluene or hexane, then the dissociation of acid in the organic phase can be disregarded, but the formation of dimers (HA) 2 is very probable [64, 239]. It is important also to account for the fact that the contacting liquid phases must be mutually saturated, but the minor constituents of inert solvents practically does not affect the values of pKa in water. The variation of ionic strenght in this case also makes it possible to study the dependence of fHA on I [59]. In certain cases partition was investigated between water and a polar and/or a solvent restricdedly mixing with water. In a polar solvent (nitrobenzene, oxydipropionitrile) dissociation of acid HA is possible [240, 241]. Compiled values of the partition constants of neutral molecules of different nature between water and organic solvent have been published [239, 242, 243]. The partition method can also be used for the analysis of the equilibrium in anhydrous system, for a pair of restrictedly miscible organic solvents, for example, for the system n-heptaneDMSO [168]. Conductometric Method Conductometric data provide a possibility to the estimation of the degree of dissociation of the electrolyte as the ratio of molar electric conductivity at a given concentration (c) to the maximum molar electric conductivity (), which is determined by extrapolation to the infinite dilution.
= c/. (23)
measurement of c of a series of solutions with different concentrations, with the introduction of corrections for the relaxation and electrophoresis effect and the ionic activity coefficients. Then a set of the parameters is calculated with best fit to the experimental phoreograms (c c). Various approaches to the calculation of dissociation constants are most compltely considered in the survey [113]. The Fuoss Kraus or Shidlovsky equations can be used for estimating the value of constants in the first approximation. It is suggested now that one of the most correct approaches is the use of LeeWheaton equation [244246] that besides other factors accounts for the dielectric saturation in the ion vicinity. The conductometric method is less reliable in the study of very weak electrolytes. Therefore it is not used for the determination of very high pKa values. By the conductometric method were determined the pKa values of ortho-nitrobenzoic acid in formamide (4.26) [198] and perchloric acid in methyl isobutyl ketone (4.5) [130], and also of 2,6-dinitro-4-chlorophenol in DMF (4.68) [138]. In the mixtures of water with different organic solvents with r no less than 30 it was possible to determine with a high accuracy the values of pKa of a series of benzoic acids by the method of Pethybridge and Taba with the use of an equation of Lee and Wheaton [247, 248]. The highest value of pKa did not exceed 6.20. The values of pKa of benzoic and acetic acids (respectively 8.11 and 8.07) in 80 vol % aqueous tetrahydrofuran (r = 19.41) were determined in [249]. Many publications reported on the conductometry of the solutions of ionophores (salts) [113, 250, to 251]. The most general problem of the interpretation of phoreograms with the low and medium values of r (including the operatio with dilute solutions of 11 electrolytes) is the possibility of existence together with the ions C+ and A of ion pairs C+A (both contact and solvent-separated), triads C+AC+ and AC+A, quadrupoles (C+A)2 and even more complex species [72, 252255]. The maximum concentration that allows disregarding of ion triads can be calculated, according to Fuoss, as cmax = 1.41014 (rT)3 mol l1 [252], although processing of experimental data often shows that even at the concentrations somewhat exceeding cmax the phoreograms can be described assuming only one equilibrium [255].
This method can be used for the evaluation of pKa of acids, and of the dissociation constants of salts used for the preparation of buffer mixtures or appearing in the course of acidbase titration. Practically the determination of the dissociation constant of an electrolyte is reduced to the
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ZEVATSKII et al.
Another
problem
c
is
unreliability
of
the
extrapolation of the ( c) plot to the infinite dilution in the case of very low c values [250]. Therefore together with attempts of the joint calculation of Kass and the data on of a given electrolyte in the solvents with the high values of r are applied and Waldens rule [72, 250, 253] is used. The problem of the product of PisargevskyWalden and Waldens rule was repeatedly discussed in the literature [72, 250, 256, 257]. It is well known, in particular, the inconsistence with the Waldens rule of small ions, for example, of alkali metals cations. A conductometric study of the dissociation of trichloroacetic acid in the watermethanol system made it possible to determine, together with the constant of the association of ions H+ and CCl3COO, the value of ; the failure of Waldens rule is obvious: the PisargevskyWalden product is reduced more than 3-fold upon transfer from the water to the mixtures rich in methanol [258]. Although the Waldens rule is unsuitable for the solvated proton, it nevertheless is used sometimes in the absence of other data [130]. More correct is to combine this rule with the data for several electrolytes in the same solvent, taking into account Kohlrausch law on the independence of ionic migration ( = + + ) [136, 230, 249]. In particular, the value of an acid HA can be found in accordance with the equation
H+ + A = (C+ + A) (C+ + X) + (H+ + X). (24)
On the basis the of BouguerLambertBeer and Firordt laws, and also from the material balance the ratio of the equilibrium concentrations of the protonated and nonprotonated forms (indicator ratio) of the studied substance can be found. The experimentally observed constant for the acid considered further as indicator (HInd) is determined at a fixed wavelength and a constant analytical concentration of indicator by the equation:
obs pKa = pa* + log H
[HInd] [Ind]
= pa* + log H
D DInd DHInd D
(25)
Here D is the optical density at the given pa* value, H DInd and DHInd are optical densities after the quantitative transformation of the indicator acid into the corresponding form (for simplicity the charges are omitted; indicator acid can be cationic, neutral, anionic, etc.). Usually the values of DInd and DHInd are measured directly at the pa* by two or more units H obs above and below the K value to be found. The data for the polybasic indicator acids are processed obs analogously when the difference in K of step equilibria is 45 units and more. In the general case the summary concentrations of the forms HInd and Ind are considered, since each of these forms can be the equilibrium mixture of free species and their associates with the components of buffer mixture. In the case uncomplicated by such effects, for example, in aqueous solution with the low ionic obs strenght, the value of K is equivalent to the m exponent of the mixed constant, K , and it can be converted into the thermodynamic value of pKa [see Eqs. (4), (5)]. For the maintenance in the aqueous solutions of a constant ionic strenght at the level 0.01 mol l1 special buffer compositions are developed for spectrophotometry [263]. If measurements are carried out in the dilute solutions of strong acids, then instead of the value of pa* in certain cases are used the H concentration values of pHc (log [H+]). Then the value of pKc is determined [Eq. (3)]. If in this case the concentrations of the acid and the indicator being investigated are commensurate, then the latter should be accounted for in the material balance at the calculation of [H+] values [105, 264]. In the case of a good resolution of absorption bands of the equilibrium forms in the visible region of spectrum and applying the measures of precaution, the value of pKa can be determined in the aqueous solutions, also at high temperature and high ionic
If the dissociation of a weak acid is complicated by the homoassociation with a simple stoichiometry (1: 1), then it is possible to find the values of pKa and Kf from the same conductometric data [259]. HA Generally, HA2 species can be considered as a form of ionic triads, and for evaluation of the constants of their formation with coductometry method several approaches are developed [135, 137, 140]. In particular, it was attempted to use the difference in the ion mobility of A and HA2 . Spectrophotometric Method The spectrophotometric method of determining pKa is based on spectral measurement of the equilibrium mixture of prototropic forms at several values of pa* H near the assumed pKa value. The basic information on the fundamentals of the method and its application in specific cases is considered in a number of publications [178, 260262].
1875
strenght, with an accuracy up to (0.0050.008), and sometimes to 0.002 [265, 266]. The use of ultraviolet part of the spectrum allows obtaining good accuracy [267], even for the case of the poorly resolved bands [268]. The basic factor determining the applicability of the spectrophotometric method is the degree of resolution of the absorption spectra of protonated and deprotonated forms. The spectra of these forms are considerably resolved for amines, heterocyclic compounds with the pyridine nitrogen atom, and for phenols, since the protonation significantly changes the structure of their chromophore. On the contrary, the spectra of protonated and nonprotonated forms of aromatic carboxylic acids are hardly distinguishable (max = 510 nm) that creates difficulties for the determination of pKa connected with the selection of the analytical wavelength and processing of the results [269, 270]. The correct selection of optimum wavelengths and the use of statistical weights results in the increase in the accuracy of the pKa determination. Also the application of a derivative [261], of two-wave spectrophotometry [271], and of factor analysis was described [261, 272]. The modern trend in the application of the spectrophotometric method with the use of photodiode matrices in combination with the separating and gradient methods includes an obligatory processing of the complete absorption spectra of the mixtures of prototropic forms (multiwavelength spectrophotometric titration) [19, 38, 45, 46, 273, 274]. Along with the standard procedure the so-called three-stimulus colorimetry based on the use of chromatic coordinates is successfully employed in a number of cases [220, 224, 229, 275278]. Sometimes for determining pKa in the ground state it is possible to use fluorescence spectra [of 279281]. From the point of view of productivity the timeconsuming preparation of a series of buffer solutions is a central disadvantage of the method; therefore at the modification of method this operation is often excluded usually to the detriment of the accuracy [37, 4345]. Even in the work with aqueous solutions the factor limiting accuracy in the pKa determination by the spectrophotometric method is the measurement of pH [178].
It is obvious that together with the determination of pKa value for the solutions with variable pH values the inverse problem can also be solved: having the available pKa value of an indicator, it is possible to estimate the acidity of solution and, therefore, the pKa value of the buffer acid [281]. At the work with a highly acidic or alkaline medium the use of acidity function (H0 or, in the general case, Hx) allows obtaining the thermodynamic values of pKa, but only when the indicator belongs to the type of compounds that have been used for the construction of the respective Hx function. Acidity functions for organic solvents are also in use [100]. When the spectrum of Hind or Ind form should necessarily be measured in the sufficiently concentrated solutions of acid or alkali, it can be distorted by both the ionic association and solvate chromic effects resulting from the strong changes in the properties of the solvent [260, 261]. In this case the real value of DHInd or DInd is regarded as unknown and it can be found together with the value Ka [261]; usually this requires some transformations of Eq. (25), and the method of least squares is applied [261, 282]. It is necessary, however, to keep in mind that this procedure does not permit revealing the possible systematic drift of the pKa values caused by the additional equilibria. The presence of isosbestic point in the absorption spectra at the variations of the acidity of the medium is a necessary, but insufficient attribute of the fact that the change in pH is not accompanied by other processes besides the single-step acidbase equilibrium of the indicator [236, 261]. The blurred isosbestic point or shift of the maximum of the band of one-color indicator serves as indication of a more complex nature of the equilibrium or of the solvatechromic effects caused by the essential variation of ionic strenght (effect of the ionic atmosphere). For the low polar media the working relation is not equation (25), but expressions that describe the acid base equilibria (6) as the case of complex formation without the use of values of pa* [64, 283]. H Furthermore, the estimation of the relative constants of acidity in the inert low polar solvents is possible by determining the constants of the exchange of a metal cation for the proton between the studied acid and a salt of standard acid (transmetallation). For example, by this method the scale of the equilibrium acidity of
1876
ZEVATSKII et al.
CH-indicators was determined in cyclohexylamine (r = 4.5) [82, 83], 1,2-dimethoxyethane [84] (r = 7.2), and in THF (r = 7.0) [284287]. The values of the logarithms of the transmetallation constants were determined with the error of 0.1 [84]. The application of metal cryptands as cations has for a goal leveling the specific character of cation anionic association (cryptate acidity scale) [94, 288 292]. In this case the cation of metal, for example, lithium, is reliably screened by macrocyclic ligand. Furthermore, a scale of acidity was recently proposed based on the spectrophotometric studies of prototropic transformations involving bulky bases of the type of phosphazenes where the specific interionnic interactions of protonated forms are extremely hindered [293]. Thus the scales in n-heptane [95] and THF [294] were built. The possibility to work with low concentrations of samples is the major advantage of the spectrophotometric method (104105 mol l1). Furthermore, there is an opportunity to reveal the formation of dimers and larger aggregates of separate prototropic forms of the studied substance observing the deviation from the BouguerLambertBeer law. But the operation with the low concentrations in the nonaqueous media is in certain cases the almost inevitable source of the complications of special kind. Since the steady values of pa* as a rule are difficult to H create without the use of buffer mixtures (including, in the general case, a solution of acid or alkali), it is necessary to consider the possibility of the unspecific (Coulomb) association of the ionic forms of indicators with the oppositely charged organic or inorganic ions of the buffer mixtures, for example, of Ind+Na or IndH+ClO4 [105]. This relates to the solvents with low r (usually r < 20) [97, 130, 295], where the ratio of the equilibrium concentrations of the anion Ind involved and not involved in the ionic associate with the cation C+, is expressed by equation
[C+Ind]/[Ind] = Kass[C+]f12, (26)
additional experiments with the addition of crown ethers for elucidation the degree of influence of the ionic association M+A [111]. On the other hand, with the NDHB solvents it is especially difficult to avoid the interfering influence of the heteroassociation proceeding due to the hydrogen bonding since the combined forms of indicator acid can associate with the components of the buffer mixture. Depending on the conditions, the complexes of different composition can be formed, for example: IndHA, IndHA, IndH+A, and so on. Sometimes these interactions cannot be reflected in the electron absorption spectra, but sometimes can be manifested distinctly as, for example, in the case of 4nitrophenolate in the benzoate buffer solutions in acetonitrile [107, 122]. Acceptable results gives the use of an unbuffered method of dilution, which is reduced to the analysis of the absorption spectra with the variation of the concentration of the indicator like, for example, picric acid or dinitrophenols that are sufficiently strongly dissociated in the pure solvent [136, 171, 175, 231, 296]. But the noticeable discrepancies in the values obtained within the same method by different authors are possible. Thus, in nitrobenzene with spectrophotometric method of dilution the value was obtained of pKa = 6.630.08 [175] which is noticeably lower than the concentration value of 7.46 published earlier [296]. The values of pKa existing in the literature for the picric acid in acetone appear to be a good illustration of the spread of data obtained by different authors and different methods. By the conductometric method were obtained the values of pKa = 3.86 [297] and 6.3 [259]. Potentiometry in the cells with liquid junction with the glass electrode gave value of 7.81 [225]. At the same time, the potentiometric and spectrophotometric method of the control of acidity gave in [106] the coinciding values: 9.20.1 and 9.260.02. Examples of these and even larger discrepancies are collected in the compilations of the values of pKa in the NDHB solvents [68, 71]. The most probable reason is the imperfection of the standar-dization of pa* H scales . The Scales of pa* and the Standards of pa* H H The validity both of the potentiometric and spectrophotometric determinations of the pKa values
where f1 is the concentration activity coefficient of the single-charged ion, Kass is the constant of the association of the ions Ind and C+. If Kass ~ 104, then already with [C+] ~ 103 mol l1 the fraction of anions of indicator bound in the associate can comprise no less than 50%. Even in the case of DMSO which is a polar solvent well solvating cations it is desirable to carry out
1877
depends on the reliability of pa* estimation. Let us H consider at first the standardization of the acidity scale, based on the emf measurements of the cells without or with liquid junction. The problem of standardization of pH measurements in aqueous solutions is solved completely enough [7, 157]. It is known that the experimental determination of the activity coefficients and activity of separate ion is impossible in principal [298]. The value of pH in the work of Bates [7] obtained from the experimental data was named instrumental value (pHinstr). Its correlation with the theoretical value is based on a number of assumptions outside of thermodynamics, accepted in this field and fixed in the recommendations of IUPAC [99, 299]. Further, at least one solution with the known value of pa* is required. First the emf of standard chain (14) H is measured, Estand., and then the emf of the same chain with the examined solution. The value of pa* is H calculated by the formula
pa* = (pa* )stand + H H E Estand . RTln 10/F (27)
solution), 4.008 (ortho-phthalate), 6.865 (phosphate), 9.180 (borate buffer solution), and 12.454 (saturated solution of calcium hydroxide) [157]. In 1980, the IUPAC Conference accepted 0.05 mol/kg solution of potassium hydrophthalate as the common primary standard. Commonly the Nernst Eq. (28) parameters E0 and k are determined on the basis of emf measurements on the cell with liquid junction containing indicated standard solutions with the glass electrode as the indicator, and then they are used for determineation of the pH of the examined solution
E = E0 k pH. (28)
As a reference electrode commonly serves the silver chloride or calomel electrode, and the connecting bridge usually is filled with saturated or unimolar aqueous potassium chloride, or with another electrolyte, whose mobilities of cation and anion are similar. In this case the question about the interpretation of measurements at the high ionic strenght of working solutions remains not completely clear, since I values of standard solutions are low, and the values of diffusion potential can be different. As to the nonaqueous solutions, for the completeness of standardization in the ideal case are needed: (a) the value of the constant of autoprotolysis, (b) as many as necessary pH standards for the sweeping over the entire scale and (c) the ws values H for constructing the common (intersolvent) acidity scale [300]. The last values are necessary for the correlation of the scales in different solvents with the aqueous pH scale, in view of the specific role of water. In the solvents with the low r values, for example, in benzene, the potentiometric method is ineffective due to the vanishingly small concentration of free ions and high electrical resistance. There are data on the pKs values of mixed solvents [157, 301]. The approximate estimate of the constants of autoprotolysis of organic solvents with so-called potentials of semineutralization was developed by Bykova and Petrov [133, 161, 302, 303]. The pH standard (reference solution for comparison) recommended by IUPAC for water organic mixtures is the solution of potassium hydrophtalate in the examined solvent at the concentration of 0.05 mol l1. In the IUPAC recommendations of 19841997 [300, 304, 305] the values of pa* for this standard in the H mixtures of water with methanol, ethanol, isopropanol,
The measurements are performed by the compensation method in order to exclude the errors due to the electrode polarization and the electrolysis. As a reference electrode calomel elctrode is sometimes used, and for the hydrogen electrode the smooth platinum surface is sometimes applied along with the platinized platinum. But for the serial measurements and in the work with the solutions of complex composition, in particular, in the presence of oxidants, the hydrogen electrode is not always convenient. On the other hand, the reference electrode can interact with the components of the solution, and the presence in the latter of ions Cl or other ions to which the reference electrode is reversible is undesirable. Therefore in practice as a rule glass electrode is used as indicator and the measurements are carried out in a cell with liquid junction. But in this case appears the uncertainty caused by the diffusion potential of the liquid connection. The standard pH solutions suitable for the calibration of cells with transference with the glass electrode were created as a result of the thorough studies based, first of all, on the use of standard cells without transference (14, 20). These solutions have recommended themselves well for many years. At 25 o C they have the values of pH 1.679 (oxalate buffer
1878
ZEVATSKII et al.
acetonitrile, 1,4-dioxane, DMSO, ethylene glycol, methoxyethanol containing up to 84% of organic solvent are listed in tables with the increments 20% on the average. Besides these primary data, in [157, 304, 301, 304306] are published the tables of the pH values of other buffer compositions (acetate, phosphate, succinate, etc.) in the same solvents, with regular renewing and extending. The tables are supplemented with empirical equations for interpolation of the values for intermediate compositions of the mixtures [304]. The pa* values of the buffer for the entire range of H the compositions of the watermethanol and water ethanol systems [7, 157, 300, 301, 306], for the mixtures of water with ethanol, 2-propanol, ethylene glycol, DMSO, acetone, 1,4-dioxane [300, 301, 305, 306], and acetonitrile [204] are published. In the Aleksandrovs monograph are tabulated the pa* values of standard buffers he measured with H coworkers for entire range of the compositions of the watermethanol system, for the mixtures of water with 2-propanol, 1,4-dioxane, acetone, DMSO, DMF, and N,N-dimethylacetamide [157]. There is the summary of published data for the other nonaqueous systems. The pa* values of these buffer systems are found H mainly on the basis of the same procedure, as for the aqueous solutions, namely, by the so-called Method of the NBS of the USA [7, 75, 157]. Essential complication here is the (possible) incomplete dissociation of hydrogen chloride and salts in the nonaqueous media [157, 307]. The constants of the corresponding equilibria must be determined preliminarily, e.g. by conductometry. In the NHBD solvents, the formation of HCl2 and more complex species is possible. The method recommended by IUPAC consists in the sequential emf measuring in two cell with liquid junction with the hydrogen electrode: one with the standard solution and other with the examined one [75]. The connecting bridge is filled with the solution of a salt that should be readily soluble and when possible dissociated in this solvent completely, for maintaining constant the value of the diffusion potential. Most often tetraalkylammonium salts, perchlorates or picrates, are used [71, 97], and if the silver chloride electrode is taken as reference elec-trode, then a mixture of silver and tetraethylammo-nium perchlorates is used. Generally speaking, the quinhydrone electrode can be used as the indicator [189]. But it cannot be applied
in the region of the high values of pa* , and the limit of H the applicability in each nonaqueous solvent must be established in the course of special experiments. As in the case of aqueous systems, at strong difference in the I values of the investigated and the standard solutions the diffusion potential can be uncompensated. Furthermore, it is necessary to make certain that the glass electrode has the correct hydrogen function by measuring the standard buffer solutions. For example, the acid and alkaline errors of glass electrode were investigated in propylene carbonate [137, 199], sulfolane [144] and in other solvents [5, 208]. Numerous potentiometric measurements in the nonaqueous (more often in the waterorganic) solvents usually are carried out with cells with liquid junction. Then, along with the calibration of chain with the mentioned above standard solutions developed for this solvent many authors use traditional aqueous standards, and the required pa* values for a given H solvent are recalculated introducing correction into the obtained instrumental values pHinstr:
pa* = pHinstr . H (29)
These corrections consist of two terms [177]: one accounts for diffusionphase potential on the water solution interphase expressed in pH units (Ej = Ej/(RTln 10/F), and the second is logws H
= Ej log ws . H (30)
The values can be found by special experiments by comparing the values of pa* of the same solution H obtained by both methods; other procedures are also possible [157, 308]. These values are determined for the most commonly used waterorganic and for some nonaqueous solvents, and they are compiled in the literature [7, 57, 194, 195, 214, 308]. The values of can be both positive and negative, and in the water organic mixtures by the absolute value usually do not exceed 12 units. The discussed approach is based on the fact that values of Ej do not depend on the solution acidity. Actualy this is not always true. For the cells with the identical composition of solvent in the right and left sides the Ej is defined only by a difference between composition and ion activities of the respective electrolytes. Otherwise it is determined also by the difference in the solvation of ions and by the dipole
1879
dipole interaction of solvents. For the waternonaqueous solvent interphase its value can reach 300 mV [71]. But for the practical measurement of pa* the H construction of measuring cell and the procedure of experiment must provide, as a minimum, the constant Ej at the calibration and a minimum drift within a series of measurements. Bates has shown [7] that the value of the liquidliquid interphase potential of the cell with liquid junction, which includes the interface waternonaqueous solvent, is satisfactorily reproducible. Application of two standards of pa* , one with H greater, and another with smaller pa* than that of the H measured solution, makes it possible to substantially decrease the error caused by the residual diffusion potential [300]. To warranty the reproducibility of Ej the construction of electrolytic bridge (liquid key) must provide reliable continuous contact and must exclude the mixing of electrolytes solutions. Usually for this purpose a glass tube is filled either with a gel or with a dense porous inert material. It is important that it would not be dissolved and would stay well inside the tube. It is desirable to use electrolite providing equal mobility of its ions in the solvents of the right and left sides of the cell. If this is impossible, then the concentration of electrolyte must be much higher than in the measuring and reference parts of the cell [300]. Although the corrections are formally determined in the organic solvents with the water content even less than 10%, the application of formula (30) for constructing the pa* scale for these media can lead to H the significant errors [157], since the first term in the formula (30) can considerably change along the acidity scale. Application of the method of IUPAC to such media is also hardly possible, because the solution of potassium hydrophthalate cannot be used as a standard in view of the low solubility and decrease in the buffer capacity in comparison with the richer in water mixtures [305]. Low solubility and/or incomplete dissociation of buffer salt also becomes serious problem for the anhydrous solvents. In such cases a convenient method of constructing the pa* scale is the use of buffer mixtures on the basis H of acids with the known values of pKa. Most successful for this are a mixture of picric acid with tetraethyl- or tetrabutilammonium picrate for the acid region and diphenylguanidinium or 1,8-diazabicyclo[5.4.0]-7-undecenium perchlorate or trifluoromethanesulfonate for the region of high pa* [71]. The calibration is also H possible with the solution of a strong (completely
dissociated) acid in the applied solvent with the known concentration. The pKa values of not too weak acids can be determined by conductometry or by spectrophotometry using the dilution method. For the solvents, where sufficiently reliable values pKa of acids exist and the complicating processes are absent, for example, in methanol, is quite possible to compute the pa* values of the corresponding buffer H mixtures according to the equation
pa* = pKa + log H cs ca + log f1, (31)
where f1 is the activity coefficient of a single-charged ion, whose value can be calculated by DebyeHueckel equation assuming complete dissociation of the buffer salt CA (for example, sodium methoxide) [309]. This is also valid for the water acetone media [310]. In the media where the salts are dissociated completely, but the formation of species HA2 is possible Eq. (31) is applicable only at the identical analytical concentrations of acid and salt. Consider, however, that Eq. (31) is correct only under the condition [C+] >> [H+]. Otherwise, if it is desirable to calculate the value of pa* of the buffer H mixture of an acid HA (not prone to the formation of HA2complexes, for example, like picric acid) and salts CA with the concentrations respectively ca and cs, then it is necessary to have available the values of the dissociation constant of acid Ka and of the constant of association of the ions of salt, Kass, and to solve Eq. (32), which follows from the law of mass action, the material balance, and the conditions of the electroneutrality:
[H+]3(KaKass 1) [H+]2[Ka(Kass ca + f12) + cs]
1 + [H+](1 KassKa)caKa f12 + Kass Ka2ca2f12 = 0.
(32)
Here the iterative procedure is used. The final [H+] value is used for finding pa* = log [H+] log f1. H The requirements for the selection of standard buffer system for the calibration of electrode system are formulated correctly in [311]. For the calibration of the electrochemical chains used in the pHmetry in the NDHB solvents it is desirable to use the buffer mixtures not prone to homoassociation. Most successful in this respect are buffers on the basis of picric acid, 2,6-dinitrophenol, and other acids with bulky ortho groups creating steric hindrances to the association [77, 137, 170].
1880
ZEVATSKII et al.
The erroneously selected reference point leads to the displacement of the scale of pa* by a constant H value which can be corrected later. But much more dangerous and practically unavoidable are the random and especially systematic errors when at the measurement the pKa in the nonaqueous media the calibration of the electrode is carried out on the buffer solutions that create in the studied medium the pa* H values by several units less than the expected pKa value of a solution under study [69, 130, 136, 172, 312]. For example, in [70, 220, 229] the calibrations in acetonitrile were carried out on picrate buffers (pKa = 11.0), and the measured values of the pKa of indicators and of benzoic acid derivatives were substantially (sometimes by 911 logarithmic units) higher. Analogously in [98] in tert-butanol the chain was graduated by the picrate buffer solutions in the region of pa* of H approximately 5, while the measurements were carried out upto pa* ~ 20. H The coefficient k in the Eq. (28) in such cases frequently differs significantly from the Nernst value (59.16 mV at 25C), although some authors a priori take it as equal to the theoretical, and find value E0 with Eq. (28) from the measurements emf of solutions with the known concentration or H+ activity, for example, in diluted HClO4 [138, 229, 313] or in picrate buffer solution [123, 199, 238]. More preferable is the calibration of the metering circuit with the buffer solutions consisting of the acids with the known values of the pKa in a given solvent comprising the largest possible range of pa* , for H example, picric acid, 2,4- and 2,6-dinitrophenol, and benzoic acid [78]. Working with one buffer acid it is possible to somewhat extend the region of the calibration of cell with liquid junction with the glass electrode by measuring emf in the course of the titration of solution of organic acid with the known pKa value by a solution of a base, for example, of benzoic acid solution in DMF by a solution of tetra-n-butylammonium hydroxide [224]. At the calibration of the cell with liquid junction with glass electrode the following procedure can be recommended. The hydrogen function of glass electrode should be cheched in a cell without liquid junction against the hydrogen electrode, using solutions with a wide range of acidity, moreover, not necessarily with the known values of pa* [191]. Being H convinced in the constancy of this chain emf over the
entire tested range or on its part, it is possible then to begin the determination of E0 and the slope of the dependence of E0 on pa* using solutions with the H known values of pa* in the acid region. H When hydrogen function of the glass electrode is checked by an appropriate method, the measurements both in the nonaqueous solvent and in the water can be carried out in the concentration scale (for example, in the aqueous solution with the high ionic strenght) [187]. In this case the relationship is used
log [H+] = pHmeasured + const. (33)
The value of the constant in the right side of Eq. (33) should be determined preliminarily by the measurement of pHmeasured in the solutions with the known values of log [H+]. In the solvents with the medium values of r (approximately from 1215 to 20) the construction of the scales of the activity of lyonium ion often becomes difficult without taking into account the incompleteness of the dissociation of salts, which makes necessary the employment of the conductometry [157]. Along with the potentiometeric method of constructing the scale of acidity also the spectrophotometric method is used based on the stepwise overlapping procedure. The values of pKa of indicators and buffer acids are determined alternately. Usually an acid strong in this solvent is taken as a reference point, in whose solutions the value of pa* H can be easily calculated. The disadvantages of the method include a necessity of using a large collection of indicators in the case of the wide pa* scale and the H inevitable accumulation of errors connected with it. Application of this method is extremely complicated when solvents with the low value of r or/and facilitating homoand heteroassociation of the dissolved substances are used. It was reported on the construction by this method of the scale of acidity in N-methylpyrrolidone and N,N-dimethylacetamide, beginning with the solutions of perchloric and ptoluenesulfonic acids that were believed to be completely dissociated [314]. The most convenient is the indicator method of overlapping at the work with the waterorganic mixtures with the sufficiently high values of r, for example, with the mixtures of water with DMSO [315, 316] and with ethanol [269]. For evaluating the acidity of highly acidic media the indicator procedure of overlapping is also used. In
1881
this case for evaluating the acidity of solutions of H2SO4, HCl, and of other acids in nonaqueous media two methods of the standardization are possible: the construction of H0 scale or of another function with the use of the pKa value of the indicator in water [317] or in the given mixed solvent [318]. Sometimes at the work with the water mixtures the values of pKa are used not in the molar scale, but in the scale of molar ratios (number of moles per 55.5 moles of solvent) [318]. Alongside the acidity functions H0, H''', and HR for the solutions of acids, the analogous scales of basicity (H, J) were built for highly basic alkaline and metal alkoxylate solutions and also for the solutions of organic bases in water and anhydrous solvents [100, 165, 319322]. All these scales of acidity can be used for the estimations of the values of pKa of very weak acids. There is a special interest in the prolongation of the scale of acidity in the protophilic solvent DMSO, where due to the poor solvation of OH and CH3SOCH2 ions even at their moderate concentration the medium becomes superbasic [164, 260, 323, 324]. In this case it is possible to determine pKa values of such organic compounds that under the normal conditions do not display acidic properties at all (for example, xanthene, triphenylmethane, etc.) [67, 112]. In the solutions of some organic acids at the addition of different quantities of potassium or sodium dimsyl in the presence of triphenylmethane an ion (C6H5)3C is formed [324]. The construction of the function of acidity Hin the solutions of potassium dimsil by the indicator procedure of overlapping made it possible to cover the region of pKa from 18.2 to 27.7 logarithmic units. CONCLUSIONS The treatment performed here of the problems of the determination of pKa in water, nonaqueous, and waterorganic media allows understanding the reasons for the low accuracy of the determination of pKa by modern rapid methods in the substantial part of the above mentioned reports [1319, 30, 38]. The inadequate results are obtained basically as a result of the errors in the construction of the pH scale and in the pH measurement [1315, 1719, 2426, 38, 325]. Similar errors are inevitable at the underestimation of the complexity of the prototropic and related processes occurring in solvent under the conditions of pKa
measuring. Furthermore, comparison of the results obtained by the rapid methods with the data obtained by traditional methods sometimes is very difficult, often since [69, 70, 130, 138, 172, 220, 229, 259, 297, 312] the causes of obtaining the incorrect values of thermodynamic constants with the traditional measurements are not entirely removed. A half century ago Palm has noted (and this is quite correct now) that solvent has a more diverse effect on the equilibrium of reactions in the solution (in this case on the pKa value) both by the nature and by the value, compared to the effects of the structure of an organic acid. The presence of any noticeable process with the participation of the terms of Eq. (2), and also the perturbations introduced by instruments in connection to the method of measurement lead to the fact that the observed value of pKa differs from the thermodynamic value by several logarithmic units. Theoretically it is possible for each measurement to write a scheme of the parallel processes, masking the target equilibrium, for example, Eq. (32). However, in practice the way of accounting for can lead to high errors in the results of measurements and often it will be necessary to prevent some processes that lead to experimental problems. The central target of this survey is to warn the researcher against possible oversights both at the development and improvement of the new methods of determining pKa and at the use of the traditional approaches. On the basis of the above said it seems reasonable to give some practical recommendations regarding the quantitative study of acidbase equilibria in the nonaqueous media: When r is below approximately 20 it is necessary to determine preliminary the dissociation constants of the corresponding salts employing both potentiometric and the spectrophotometric methods. At the potentiometric determination of pKa in polar NDHB solvents the accounting for homoassociation is necessary; in the case of formation of simplest complex of HA2 type the value of pKa can be evaluated without the preliminary determination of the constant of homoassociation. However at the spectrophotometric determination of pKa of indicator acids in buffer solutions in the NDHB solvents it is practically impossible to avoid heteroassociation.
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REFERENCES
1. Babic, S.A. Horvat, J.M., Mutavdzic-Pavlovic, D., and Kastelan-Macan, M., Trends Anal. Chem., 2007, vol. 26, no. 11, p. 1043. 2. Tehan, B.G., Lloyd, E.J., Wong, M.G., Pitt, W.R., Gancia, E., and Manallack, D.T., Quant. Struct.-Act. Relat., 2002, vol. 21, no. 5, p. 473. 3. Jelfs, S., Ertl, P., and Selzer, P., J. Chem. Inf. Model., 2007, vol. 47, no. 2, p. 450. 4. Avdeef, B. and Testa, G., Cell. Mol. Life Sci., 2002, vol. 59, no. 10, p. 1681. 5. Izmailov, N.A., Elektrokhimiya rastvorov (Electrochemistry of solutions), Kharkov: Kharkov. Gos. Univ., 1976. 6. Reichardt, C., Solvents and Solvent Effects in Organic Chemistry, WeinHeim: Wiley, 2003. 7. Beits, R., Opredelenie pH (Measuring pH), Leningrad: Khimiya, 1972. 8. Izmailov, N.A. and Shatenshtein, A.I., Izotopnyi obmen i zameshchenie vodoroda v organicheskikh soedineniyakh (Isotope Exhange and Hydrogen Substitution in Organic Compounds), Moscow: Izd. Akad. Nauk SSSR, 1960. 9. Mchedlov-Petrossyan, N.O., J. Molec. Liquids, 2009, vol. 145, no. 3, p. 110. 10. Jover, J., Bosque, R., and Sales, J., QSAR Comb. Sci., 2007, vol. 26, no. 3, p. 385. 11. Jover, J., Bosque, R., and Sales, J., QSAR Comb. Sci., 2008, vol. 27, p. 563. 12. Jover, J., Bosque, R., and Sales, J., QSAR Comb. Sci., 2008, vol. 27, no. 10, p. 1179. 13. Sancho, M.I., Jubert, A.H., Blanco, S.E., Ferretti, F.H., and Castro, E.A., Can. J. Chem., 2008, vol. 86, no. 1, p. 462. 14. Wiczling, P., Kawczak, P., Nasal, A., and Kaliszan, R., Anal. Chem., 2006, vol. 78, no. 1, p. 239. 15. Markuszewski, M.J., Wiczling, P., and Kaliszan, R., Comb. Chem. High Throughput Screening, 2004, vol. 7, no. 4, p. 281. 16. Erdemgil, F.Z., Sanli, S., Sanli, N., Oezkan, G., Barbosa, J., Guiteras, J., and Beltran, J.L., Talanta, 2007, vol. 72, no. 2, p. 489. 17. Beltrn, J.L., Sanli, N., Fonrodona, G., Barrn, D., zkan, G., and Barbosa, J., Anal. Chim. Acta, 2003, vol. 484, no. 2, p. 253. 18. Sanz-Nebot, T., Toro, I., and Barbosa, J., J. Chromatography, A, 2001, vol. 933, p. 45. 19. Wan, H., Holmen, A.G., Wang, Y., Lindberg, W., Englund, M., Nagard, M.B., and Thompson, R.A., Rapid Comm. Mass Spectrom., 2003, vol. 17, no. 23, p. 2639.
20. Jia, Z., Ramstad, T., and Zhong, M., Electrophoresis, 2001, vol. 22, no. 6, p. 1112. 21. Foulon, C., Danel, C., Vaccher, C., Yous, S., Bonte, J.P., and Goossens, J.-F., J. Chromatography, A, 2004, vol. 1035, no. 1, p. 131. 22. Cantu, M.D., Hillebrand, S., and Carrilho, E., J. Chromatography A, 2005, vol. 1068, no. 1, p. 99. 23. Riekkola, M.-L., Electrophoresis, 2002, vol. 23, nos. 22 23, p. 3865. 24. Porras, S.P. and Kenndler, E., J. Chromatography, A, 2004, vol. 1037, nos. 12, p. 455. 25. Porras, S.P., Riekkola, M.L., and Kenndler, E., J. Chromatography A, 2001, vol. 905, nos. 12, p. 259. 26. Porras, S.P. and Kenndler, E., Electrophoresis, 2004, vol. 25, p. 2946. 27. Grispony, G., Casu, M., Nurchi, V.M., CesareMirincola, F., Pivetta, T., and Silvagni, R., Talanta, 2002, vol. 56, no. 3, p. 441. 28. Rabenstein, D.L., Hari, S.P., and Kaerner, A., Anal. Chem., 1997, vol. 69, no. 21, p. 4310. 29. Liu, T., Ryan M., Dahlquist, F.W., and Griffith, O.H., Protein Science, 1997, vol. 6, no. 9, p. 1937. 30. Gomez-Zaleta, B., Ramirez-Silva, M.T., Guterrez, A., Gonzalez-Vergara, E., Guizado-Rodriguez, M., and Rojas-Hernandez, A., Spectrochimica Acta, A, 2006, vol. 64, no. 4, p. 1002. 31. Luptak, A., Ferre-DAmare, A.R., Zhou, K., Zilm, K.W., and Doudna, J.A., J. Am. Chem. Soc., 2001, vol. 123, no. 35, p. 8447. 32. Palalikit, D. and Block, J., Anal. Chem., 1980, vol. 52, no. 4, p. 624. 33. Beckers, J.L., Everaerts, F.M., and Ackermans, M.T., J. Chromatogr., 1991, vol. 537, no. 3-4, p. 407. 34. Gluck, S.J. and Cleveland, J.A., J. Chromatography A, 1994, vol. 680, no. 14, p. 43. 35. Ionin, B.I., Ershov, B.A., and Koltsov, A.I., YaMRspektroskopiya v organicheskoi khimii (NMR Spectroscopy in Organic Chemistry), Leningrad: Khimiya, 1983. 36. Hardcastle, J.E. and Jano, I., J. Chromatogr., B, 1998, vol. 717, no. 1, p. 39. 37. Szakcs, Z. and Hgele, G., Talanta, 2004, vol. 62, no. 4, p. 819. 38. Currie, C.A., Heineman, W.R., Halsall, H.B., Seliskar, C.J., Limbach, P.A., Arias, F., and Wehmeyer, K.R., J. Chromatography, B, 2005, vol. 824, nos. 12, p. 201. 39. Foulon, C., Duhal, N., Lacroix-Callens, B., Vaccher, C., Bonte, J.P., and Goossens, J.F., Eur, J. Pharm. Sci., 2007, vol. 31, no. 3-4, p. 165. 40. Andrasi, M., Buglyo, P., Zekany, L., and Gaspar, A., J. Pharm. Biomed. Anal., 2007, vol. 44, p. 1040. 41. Barbosa, J., Barrun, D., Jimenez-Loza, N., E., and SanzNebot, V., Anal. Chim. Acta, 2001, vol. 437, p. 309.
CONTHEMPORARY METHODS FOR THE EXPERIMENTAL DETERMINATION 42. Shamsipur, M., Maddah, B., Hemmateenejad, B., Rouhani, S., Haghbeen, K., and Alizadeh, K., Spectrochim. Acta, A, 2008, vol. 70, no. 1, p. 1. 43. Derya, K. and Mahir, A., Spectrochim. Acta, 2000, vol. 56, no. 14, p. 2753. 44. Takacs-Novak, K. and Tam, K.Y., Anal. Chim. Acta, 2001, vol. 434, no. 1, p. 157. 45. Mitchell, R.C., Salter, C.J., and Tam, K.Y., J. Pharm. Biomed. Anal., 1999, vol. 20, nos. 12, p. 289. 46. Box, K., Bevan, C., Comer, J., Hill, A., Allen, R., and Reynolds, D., Anal. Chem., 2003, vol. 75, no. 4, p. 883. 47. Abbaspour, A., Kamyabi, M.A., Khalafi-Nezhad, A., and Soltani Rad, M.N., J. Chem. Eng. Data, 2003, vol. 48, no. 4, p. 911. 48. Volgyi, G., Ruiz, R., Box, K., Comer, J., Bosch, E., and Takacs-Novak, K., Anal. Chim. Acta, 2007, vol. 583, no. 2, p. 418. 49. Anilanmert, B., Ozdemir, F.A., Erdinc, N., and Pekin, M., Mendeleev Comm., 2006, vol. 16, no. 2, p. 97. 50. Qiang, Z. and Adams, C., Water Research, 2004, vol. 38, no. 12, p. 2874. 51. Kim, S.-H. and Noh, Y.S., Bull. Korean Chem. Soc., 1998, vol. 19, no. 8, p. 822. 52. Robinson, R. and Stoks, R., Rastvory elektrolitov (Solutions of Electrolytes), Moscow: Inostrannaya Literatura, 1963. 53. Kortm, G., Vogel, W., and Andrussow, K., Pure Appl. Chem., 1960, vol. 1, nos. 23, p. 187. 54. Kortm, G., Vogel, W., and Andrussow, K., Dissociation Constants of Organic in Aqueous Solution, London, 1961. 55. Perrin, D.D., Dissociation Constants of Organic Bases in Aqueous Solutions, London: Butterworths, 1965. 56. Silln, L.G. and Martell, A.E., Stability Constants of Metal-Ion Complexes, London, 1964. 57. Silln, L.G. and Martell, A.E., Stability Constants, Suppl. no. 1. Special Publ., no. 25, London: 1971. 58. Martell, A. and Smith, R., Critical Stability Constants, vol. 5, New York: Plenum Press, 1982. 59. Komar, N.P., Zh. Anal. Khim., 1975, vol. 30l, no. 10, p. 421. 60. Kortum, G. and Sillen, L.G., Pure Appl. Chem., 1984, vol. 56, no. 2, p. 247. 61. Svg, I., Kiss, T., and Gergely, A., Pure Appl. Chem., 1993, vol. 65, no. 5, p. 1029. 62. Berthon, G., Pure Appl. Chem., 1995, vol. 67, no. 7, p. 1117. 63. Langes Handbook of Chemistry, 15th Edition, John, A., Ed., Dean, McGrawHill, 1999. 64. Davis, M.M., Acid-Base Behavior in Aprotic Organic Solvents, NBS Monograph, 105, 1968. 65. Bykova, L.N. and Petrov, S.I., Usp. Khim.., 1970, vol. 39, no. 9, p. 1631.
1883
66. Bell, R., Proton v khimii (Proton in Chemistry), Moscow: Mir, 1977. 67. Bordwell, F.G., Acc. Chem. Res., 1988, vol. 21, no. 12, p. 456. 68. Izutsu, K., Acid-Base Dissociation Constants in Dipolar Aprotic Solvents, IUPAC, Blackwell Scientific Publications, Oxford: 1990. 69. Bartnicka, H., Bojanowska, L., and Kalinowski, M.K., Austr. J. Chem., 1991, vol. 44, no. 8, p. 1077. 70. Bartnicka, H., Bojanowska, L., and Kalinowski, M., Austr. J. Chem., 1993, vol. 46, no. 1, p. 31. 71. Izutsu, K., Electrochemistry in Nonaqueous Solutions, Weinheim: Wiley-VCH Verlag, 2002. 72. Fialkov, Yu.Ya., Rastvoritel, kak sredstvo upravleniya khimicheskim protsessom (Solvents as Means for Control Over Chemical Process), Leningrad: Khimiya, 1990. 73. Kalidas, C., Hefter, G., and Marcus, Y., Chem. Rev., 2000, vol. 100, no. 3, p. 819. 74. Laitinen, G.A. and Kharris, V.E., Khimicheskii analiz (Chemical Analysis), Moscow: Khimiya, 1979. 75. Bates, R.G., Solute-Solvent Interactions, Coetzee, J.F. and Ritchie, C.D., Eds., New York, 1969, Ch. 2, p. 45. 76. Bordwell, F.G., McCallum, R.J., and Olmstead, W.N., J. Org. Chem., 1984, vol. 49, no. 8, p. 1424. 77. Kolthoff, I.M., Anal. Chem., 1974, vol. 46, no. 13, p. 1992. 78. Ludwig, M., Baron, V., Kalfus, K., Pytela, O., and Veea, M., Coll. Czech. Chem. Comm., 1986, vol. 51, no. 10, p. 2135. 79. Mchedlov-Petrosyan, N.O., Differentsirovanie sily organicheskikh kislot v istinnykh i organizovannykh rastvorakh (Differentiation of the Strength of Organic acids in Real and Organized Solutions), Kharkov: Kharkov. Gos. Unov., 2004. 80. Dyumaev, K.M. and Korolev, B.A., Usp. Khim., 1980, vol. 49, no. 11, p. 2065. 81. Kolthoff, I.M., Chantooni, M.K., and Bhowmik, S., J. Am. Chem. Soc., 1968, vol. 90, no. 1, p. 23. 82. Streitwieser, A., Hammons, J.H., Ciuffarin, E., and Brauman, J.I., J. Am. Chem. Soc., 1967, vol. 89, no. 1, p. 59. 83. Streitwieser, A., Ciuffarin, E., and Hammons J.J.H., J. Am. Chem. Soc., 1967, vol. 89, no. 1, p. 63. 84. Petrov, E.S., Terekhova, M.I., and Shatenshtein, A.I., Zh. Obshch. Khim., 1973, vol. 44, no. 5, p. 1119. 85. Hall, H.K., J. Phys. Chem., 1956, vol. 60, p. 63. 86. Izmailov, N.A. and Spivak, L.L., Zh. Fiz. Khim., 1962, vol. 36, no. 4, p. 757. 87. Izmailov, N.A. and Spivak, L.L., Zh. Fiz. Khim., 1962, vol. 36, no. 6, p. 1158.
1884
ZEVATSKII et al. 112. Valter, V., Chem. Listy, 1986, vol. 80, p. 918. 113. Safonova, L.P. and Kolker, A.M., Usp. Khim., 1992, vol. 61, no. 9, p. 1748. 114. Purlee, E.L. and Grunwald, E., J. Am. Chem. Soc., 1957, vol. 79, p. 1366. 115. Fengchun, H. and Gilkerson, W.R., J. Solution Chem., 1983, vol. 12, p. 161. 116. Kendrick, K.L. and Gilkerson, W.R., J. Solution Chem., 1986, vol. 15, p. 253. 117. Gilkerson, W.R. and McCaskill, R.A., J. Am. Chem. Soc., 1980, vol. 102, p. 5181. 118. Gilkerson, W.R. and Kendrick, K.L., J. Phys. Chem., 1984, vol. 88, p. 5352. 119. Arnaud-Neu, F., Delgado, R., and Chaves, S., Pure Appl. Chem., 2003, vol. 75, no. 1, p. 71. 120. IUPAC Compendium of Chemical Terminology, Electronic Version, http://goldbook.iupac.org 121. Kolthoff, I., M., Bruckenstein, S., and Chantooni, M.K., J. Am. Chem. Soc., 1961, vol. 83, no. 19, p. 3927. 122. Kolthoff, I.M., Chantooni, M.K., and Bhowmik, S., J. Am. Chem. Soc., 1966, vol. 88, no. 23, p. 5430. 123. Pawlak, Z., Nowak, B., and Fox, M.F., J. Chem. Soc., Faraday Trans. 1, 1982, vol. 78, p. 2157. 124. Okada, T., Chem. Commun., 1996, no. 15, p. 1779. 125. Chmurzyski, L. and Liwo, A., J. Chem. Soc., Faraday Trans., 1991, vol. 87, no. 24, p. 3853. 126. Korolev, B.A., Osmolovskaya, L.A., and Dyumaev, K.M., Zh. Obshch. Khim., 1978, vol. 48, no. 10, p. 2358. 127. Korolev, B.A., Osmolovskaya, L.A., and Dyumaev, K.M., Zh. Obshch. Khim., 1979, vol. 49, no. 4, p. 898. 128. Chmurzyski, L., J. Chem. Soc., Faraday Trans., 1991, vol. 87, no. 11, p. 1729. 129. Kolthoff, I.M. and Chantooni, M.K., J. Am. Chem. Soc., 1965, vol. 87, no. 20, p. 4428. 130. Juillard, J. and Kolthoff, I.M., J. Phys. Chem., 1971, vol. 75, no. 16, p. 2496. 131. Kolthoff, I.M. and Chantooni, M.K., J. Am. Chem. Soc., 1965, vol. 87, no. 20, p. 315. 132. Stepanov, B.I., Korolev, B.A., and Bokanov, A.I., Zh. Obshch. Khim., 1969, vol. 39, no. 2, p. 316. 133. Bykova, L.N. and Petrov S.I., Usp. Khim., 1972, vol. 41, no. 11, p. 2065. 134. Barabanov, V.P., Tretyakova, A.Ya., and Kharrasova, F.M., Zh. Obshch. Khim., 1978, vol. 48, no. 7, p. 1517. 135. Bakholdina, L.A. and Evstratova, K.I., Zh. Obshch. Khim., 1984, vol. 54, no. 10, p. 2170. 136. Kolthoff, I.M., Chantooni, M.K., and Smagowski, H., Anal. Chem., 1970, vol. 42, no. 13, p. 1622.
88. Jasinski, T., El-Harakany, A.A., Taha, A.A., and Sadek, H., Croat. Chim. Acta, 1977, vol. 49, no. 4, p. 767. 89. Popovych, O., J. Phys. Chem., 1962, vol. 66, no. 5, p. 915. 90. Tsarevskaya, M.N., Ukr. Khim. Zh., 1965, vol. 31, p. 683. 91. Tsarevskaya, M.N. and Drupova, V.I., Zh. Fiz. Khim., 1974, vol. 48, p. 2416. 92. Andreeva, A.A. and Tsarevskaya, M.N., Zh. Fiz. Khim., 1973, vol. 47, no. 10, p. 2594. 93. Denesh, I., Titrovanie v nevodnykh sredakh (Titration in Non-Aqueous Media), Moscow: Mir, 1971. 94. Antipin, I.S., Vedernikov, A.N., and Konovalov, A.I., Zh. Obshch. Khim., 1989, vol. 25, no. 1, p. 3. 95. Room, E.-I., Kaljurand, I., Leito, I., Rodima, T.I., Koppel, A., and Vlasov, V.M., J. Org. Chem., 2003, vol. 68, p. 7795. 96. Aleksandrov, V.V., Tychina, O.N., and Berezhnaya, T.A., Mchedlov-Petrossyan, N.O., J. Mol. Liquids, 2002, vol. 100, no. 3, p. 255. 97. Marple, L. and Fritz, J.S., Anal. Chem., 1963, vol. 35, no. 9, p. 1223. 98. Barbosa, J., Bosch, E., and Roses, R., Analyst., 1987, vol. 112, no. 2, p. 179. 99. Covington, A.K., Bates, R., G., and Durst, R.A., Pure Appl. Chem., 1985, vol. 57, p. 531. 100. Cox, R.A. and Yates, K., Can, J. Chem., 1983, vol. 61, no. 10, p. 2225. 101. Pytela, O. and Vetenik, P., Coll. Czech. Chem. Comm., 1983, vol. 48, no. 8, p. 2368. 102. Wojcik, J.F., J. Phys. Chem., 1985, vol. 89, no. 9, p. 1748. 103. Mchedlov-Petrosyan, N.O. and Kholin, Yu.V., Zh. Prikl. Khim., 2004, vol. 77, no. 3, p. 421. 104. Pocker, Y., J. Chem. Soc., 1958, p. 240. 105. Coetzee, J.F. and McGuire, D.K., J. Phys. Chem., 1963, vol. 67, no. 9, p. 1810. 106. Foltin, F. and Majer, P., Coll. Czech. Chem. Comm., 1978, vol. 43, p. 95. 107. Kolthoff, I.M., Chantooni, M.K., and Bhowmik, S., Anal. Chem., 1967, vol. 39, no. 3, p. 315. 108. Bordwell, F.G. and Algrim, D.J., J. Am. Chem. Soc., 1988, vol. 110, no. 9, p. 2964. 109. Bordwell, F.G. and Harrelson, L.A., Can. J. Chem., 1990, vol. 68, no. 10, p. 1714. 110. Bordwell, F.G. and Zhang, X.-M., J. Phys. Org. Chem., 1995, vol. 8, p. 529. 111. Matveeva, A.G. Terekhova, M.I., Nesterova, N.I. Petrov, E.S., Matrosov, E.I., and Kabachnik, M.I., Izv. Akad. Nauk SSSR, 1988, no. 9, p. 2067.
CONTHEMPORARY METHODS FOR THE EXPERIMENTAL DETERMINATION 137. Izutsu, K., Kolthoff, I.M., Kujinara, T., Hattori, M., and Chantooni, M., K., Anal. Chem., 1977, vol. 49, no. 3, p. 503. 138. Korolev, B.A. and Kashkovskaya, E.I., Zh. Obshch. Khim., 1979, vol. 49, no. 4, p. 909. 139. Pawlak, Z., Magoski, J., and Strohbusch, F., J. Chem. Soc., Faraday Trans. 1, 1985, vol. 81, p. 2021. 140. Kolthoff, I.M. and Chantooni, M.K., J. Phys. Chem., 1966, vol. 70, no. 3, p. 856. 141. Coetzee, J.F. and Cunningham, G.P., J. Am. Chem. Soc., 1965, vol. 87, no. 12, p. 2534. 142. Sttinger, R. and Strohbusch, F., Ber. Bunsenges. Phys. Chem., 1984, vol. 88, no. 8, p. 744. 143. Porras, S.P. and Kenndler, E., Electrophoresis, 2005, vol. 26, no. 17, p. 3279. 144. Coetzee, J.F. and Bertozzi, R., J. Anal. Chem., 1973, vol. 45, no. 7, p. 1064. 145. Kochergina, A.A., Evstratova, K.I., Tarasov, B.P., and Fedorov, G.F., Zh. Obshch. Khim., 1976, vol. 46, no. 5, p. 1141. 146. Kozachenko, G., Candidate Sci. (Chem.) Dissertation, Moscow, 1977. 147. Smagowski, N. and Wawrzyniak, G., Pol. J. Chem., 1982, vol. 56, no. 1, p. 201. 148. Kolthoff, I.M. and Chantooni, M.K., J. Phys. Chem., 1962, vol. 66, p. 1675. 149. Weisberger, A., Proskauer, E., Riddick, J., and Tups, E., Organicheskie rastvoriteli (Organic Solvents), London: Clarendon, 1935. Moscow: Inostrannaya Literatura, 1958. 150. Gordon, A.J. and Ford, R.A., The Chemists Companion. A Handbook of Practical Data, Techniques and References, New York: Wiley, 1972. 151. Heublein, G. and Bauerfeind, D., J. Prakt. Chem., 1982, vol. 324, no. 6, p. 882. 152. Coetzee, J.F. and Chang, T.-H., Pure Appl. Chem., 1985, vol. 57, no. 4, p. 633. 153. Marcus, Y. and Glikberg, S., Pure Appl. Chem., 1985, vol. 57, no. 6, p. 855. 154. Fujinaga, T. and Izutsu, K., Pure Appl. Chem., 1971, vol. 27, nos. 12, p. 273. 155. Reddy, T.B., Pure Appl. Chem., 1971, vol. 25, no. 2, p. 457. 156. Coetzee, T.V., Pure Appl. Chem., 1966, vol. 13, no. 3, p. 427. 157. Aleksandrov, V.V., Kislotnost nevodnykh rastvorov (Acidity of Non-Aqueous Solutions), Kharkov: Vysshaya Shkola, 1981. 158. Mandel, M. and Decroly, P., Trans. Faraday Soc., 1960, vol. 56, p. 29. 159. Sheinin, V.B. and Ivanova, Yu.B., Zh. Fiz. Khim., 2007, vol. 81, no. 8, p. 1419.
1885
160. Miron, R.R. and Hercules, D.M., Anal. Chem., 1961, vol. 33, no. 12, p. 1770. 161. Bykova, L.N. and Petrov, S.I., Zh. Anal. Khim., 1970, vol. 25, no. 1, p. 5. 162. Kratochvil, B., Anal. Chem., 1976, vol. 48, no. 5, p. 355. 163. Geil, J.V. and Reger, H., Labor Praxis, 1983, vol. 7, no. 12, p. 1264. 164. Ritchie, C.D. and Uschold, R.E., J. Am. Chem. Soc., 1967, vol. 89, no. 12, p. 2960. 165. Kaljurand, I., Rodima, T., Leito, I., Koppel, I.A., and Schwesinger, R., J. Org. Chem., 2000, vol. 65, no. 19, p. 6202. 166. Fritz, J.S. and Burgett, C.A., Anal. Chem., 1972, vol. 44, no. 9, p. 1673. 167. Schertz, W.L. and Christian, G.D., Anal. Chem., 1972, vol. 44, no. 4, p. 755. 168. Benoit, R.L., Lefebvre, D., and Frchette, M., Can. J. Chem., 1987, vol. 65, p. 996. 169. Fiezer, L.F. and Fiezer, M., Reagents for Organic Synthesis, New York: Willey, 1968. 170. Kolthoff, I.M. and Chantooni, M.K., Jr., J. Am. Chem. Soc., 1969, vol. 91, no. 25, p. 6907. 171. Mchedlov-Petrosyan, N.O., Filatov, D.Yu., Goga, S.T., and Lebed, A.V., Dokl. Nat. Akad. Nauk Ukrainy, 2008, no. 9, p. 121. 172. Kolthoff, I.M., Bhowmik, S., and Chantooni, M.K., Proc. Nat. Acad. Sci. USA, 1966, vol. 56, no. 5, p. 1370. 173. Bates, R.G., Paabo, M., and Robinson, R.A., J. Phys. Chem., 1963, vol. 67, p. 1833. 174. Kozkov, E. and Csfalvayov, B., Chem. Zvesti, 1980, vol. 34, no. 5, p. 610. 175. Barrn, D., Buti, S., and Barbosa, J., Anal. Chim. Acta, 2000, vol. 403, p. 349. 176. Ludwig, M., Pytela, O., and Veea, M., Pardubice: Collection of Papers on Non-Aqueous Solutions, 1984, vol. 46, p. 81. 177. Mollin, J., Pavelek, Z., Navratilov, J., and Recmanov, A., Coll. Czech. Chem. Commun., 1985, vol. 50, p. 2670. 178. Nikolskii, B.N. and Palchevskii, V.V., Spektroskopicheskie metody v khimii kompleksnykh soedinenii (Spectral Methods in Chemistry of Complex Compounds), Moscow: Khimiya, 1964, p. 74. 179. Gordon, J., Organicheskaya khimiya rastvorov elektrolitov (Organic Chemistry of Solutions of Electrolytes), Moscow: Mir, 1979. 180. Meloun, M. and Kotrl, S., Coll. Czech. Chem. Commun., 1977, vol. 42, no. 7, p. 2115. 181. Wooten, L.A. and Hammett, L.P., J. Am. Chem. Soc., 1935, vol. 57, p. 2289.
1886
ZEVATSKII et al. 204. Rondinni, S. and Nese, A., Electrochim. Acta, 1987, vol. 32, no. 10, p. 1499. 205. Cray, F.M. and Westrip, G.M., Trans. Faraday Soc., 1925, vol. 21, p. 326. 206. Nikolskii, B.P., Shults, M.M., and Belyustin, A.A., Vestnik Leningrad. Gos. Univ., Ser. Fiziki i Khimii, 1963, no. 4, p. 86. 207. Nikolskii, B.P. and Shults, M.M., Zh. Fiz. Khim., 1962, vol. 34, no. 6, p. 1327. 208. Izmailov, N.A., Izbrannye trudy (Selected Papers), Kiev: Naukova Dumka, 1967. 209. Covington, A.K., Butikofer, H.P., Camoes, M.F.G.F.C., Ferre, M.I.A., and Rebelo, M.J.F., Pure. Appl. Chem., 1985, vol. 57, no. 6, p. 887. 210. Avdeef, A. and Bucher, J.J., Anal. Chem., 1978, vol. 50, p. 2137. 211. Tomisic, V., Gopurenko, T., Majorinc, K., and Simeon, V., Croat. Chim. Acta, 2006, vol. 79, no. 4, p. 613. 212. Pungor, E., Toth, K., Klatsmanyi, P., G., and Izutsu, K., Pure. Appl. Chem., 1983, vol. 55, no. 12, p. 2029. 213. Izmailov, N.A. and Frantsevich-Zabludovskaya, T.F., Zh. Obshch. Khim., 1945, vol. 15, no. 4-5, p. 283. 214. van Veen, A., Hoefnagel, A.J., and Wepster, B.M., Chem. Zvesti, 1980, vol. 34, no. 5, p. 610. 215. Csfalvoyov, B., Kozkov, E., and Kluiariva, A., Acta, F.R.N. Univ. Comenianae. Chimia, 1984, vol. 32, p. 17. 216. Kalfus, K., Friedl, Z., and Exner, O., Coll. Czech. Chem. Commun., 1984, vol. 49, no. 1, p. 179. 217. Kolthoff, I.M., and Chantooni, M.K., Anal. Chem., 1978, vol. 50, no. 11, p. 1440. 218. Petrov, S.M., and Bogolyuk, G.B., Izv. Vuzov SSSR, Ser. Khimiya i Khim. Tekhnol., 1979, vol. 22, p. 1205. 219. Smolova, N.T., Zh. Fiz. Khim., 1980, vol. 54, no. 8, p. 1978. 220. Barbosa, J., Bosch, E., and Surez, F., Analyst, 1985, vol. 110, p. 1473. 221. Bosch, E., Rfols, C., and Ross, M., Talanta, 1989, vol. 36, no. 12, p. 1227. 222. Fritz, J.S., and Marple, L., Anal. Chem., 1962, vol. 34, no. 8, p. 921. 223. Simonova, O.R., Sheinin, V.B., and Berezin, B.D., Zh. Analit. Khim., 2007, vol. 62, no. 7, p. 757. 224. Barbosa, J. and Bosch, C.M., Talanta, 1991, vol. 38, no. 11, p. 1297. 225. Aufauvre, E., Bull. Soc. Chim. France, 1967, no. 8, p. 2802. 226. Barabanov, V.P., Tsentovskii, V.M., Tretyakova, A.Ya., Zagidullina, O.Sh., Kharrasova, F.M., Erre, E.A., and Rakhimova, G.I., Zh. Obshch. Khim., 1972, vol. 42, no. 11, p. 2431.
182. Kharned, G. and Owen, B., Fizicheskaya khimiya rastvorov elektrolitov (Physical Chemistry of Solutions of Electrolytes), Moscow: Inostrannaya Literatuta, 1952. 183. Petrov, S.M. and Umanskii, Yu.I., Zh. Fiz. Khim., 1967, vol. 41, no. 6, p. 1374. 184. Dash, U.N., Austr., J. Chem., 1975, vol. 28, p. 1653. 185. Acharya, K. and Nayak, B., Electrochim. Acta, 1983, vol. 28, no. 8, p. 1041. 186. Schwitzgebel, G., Z. Phys. Chem., NF, 1981, vol. 125, p. 1. 187. Bek, M. and Nadpal, I., Issledovanie kompleksoobrazovaniya noveishimi metodami (Complexation Investigation by Newest Methods), Moscow: Mir, 1989. 188. Chernovyants, M.S., Askalepova, O.I., Shcherbakov, I.N., and Bagdasarov, K.N., Zh. Anal. Khim., 1991, vol. 46, no. 3, p. 608. 189. Izmailov, N.A. and Zabara, I.F., Collection of Papers on Physical Chemistry, Moscow: Akad. Nauk SSSR, 1947, p. 310. 190. Izmailov, N.A. and Izmailova, V.N., Zh. Fiz. Khim., 1955, vol. 29, no. 6, p. 1050. 191. Grigoreva, A.A. and Spivak, L.L., Zh. Fiz. Khim., 1970, vol. 44, no. 2, p. 440. 192. Loginova, L.P. and Lycheva, O.S., Khim. Fizika, 1996, vol. 15, no. 11, p. 97. 193. Kolthoff, I.M. and Thomas, F.G., J. Phys. Chem., 1965, vol. 69, p. 3049. 194. Douheret, G., Bull. Soc. Chim. Fr., 1967, vol. 4, p. 1412. 195. Douheret, G., Bull. Soc. Chim. Fr., 1968, vol. 8, p. 3122. 196. Chernysheva, G.M., Kutyrev, I.M. and Basargin, N.N., Zh. Anal. Khim., 1997, vol. 52, no. 8, p. 808. 197. Gelsema, W.J. de Ligny, C.L. and Visserman, M.G.F., Rec. Trav. Chim., 1965, vol. 84, nos. 916, p. 1129. 198. Verhoek, F.H., J. Am. Chem. Soc., 1936, vol. 58, no. 12, p. 2577. 199. Nedvetskaya, G.B., Shevtsova, I.Ya., and Baranov, N.A., Zh. Obshch. Khim., 1984, vol. 54, no. 8, p. 1681. 200. Everett, D.H. and Rasmussen, S.E., J. Chem. Soc., 1954, no. 8, p. 2812. 201. Feakins, D. and French, C.M., J. Chem. Soc., 1956, p. 3168; Sen, L.H., Anal. Chim. Acta., 1970, vol. 50, p. 287; Kozakova, E., Majersky, P. and Pal, J., Chem. Papers, 1986, vol. 40, no. 4, p. 543. 202. Kozkova, E., Kozk, J. and Groidlov, A., Chem. Zvesti, 1982, vol. 36, no. 4, p. 507. 203. Bax, D., de Ligny, C.L., Alfenaar, M., and Mohr, M.J., Rec. Trav. Chim., 1972, vol. 91, no. 4, p. 601.
CONTHEMPORARY METHODS FOR THE EXPERIMENTAL DETERMINATION 227. Barabanov, V.P., Tsentovskii, V.M. and Tretyakova, A.Ya., Zh. Fiz. Khim., 1973, vol. 47, no. 12, p. 2316. 228. Kolthoff, I.M. and Chantooni, M.K., J. Am. Chem. Soc., 1973, vol. 95, no. 26, p. 8539. 229. Barbosa, J., Ross, M., and Sanz-Nebot, V., Talanta, 1988, vol. 35, no. 12, p. 1013. 230. Baranov, N.A., Manukhina, G.B., and Vlasov, N.A., Zh. Fiz. Khim., 1979, vol. 53, no. 10, p. 2634. 231. Matrosov, E.I., Kozachenko, A.G., and Kabachnik, M.I., Izv. Akad. Nauk SSSR. Ser. Khim., 1976, no. 2, p. 313. 232. Malmstadt, H.V. and Vassallo, D.A., Anal. Chem., 1959, vol. 31, no. 5, p. 862. 233. Riddick, J.A., Anal. Chem., 1960, vol. 32, no. 5, p. 172. 234. Kim, J.I., Cecal, A., Born, H.-J., and Gomaa, E.A., Z. Phys. Chem. NF, 1978, vol. 110, p. 209. 235. Kim, J.I., Z. Phys. Chem. NF., 1978, vol. 113, p. 129. 236. Albert, A. and Sergent, E.P., Ionization Constants of Acids and. Bases, New York: Wilcy, 1962. 237. Barabanov, V.P., Tsentovskii, V.M., Tretyakova, A.Ya., Kharrasova, F.M., and Breenkova, V., Zh. Obshch. Khim., 1973, vol. 43, no. 5, p. 1147. 238. Pawlak, Z. and Nowak, B., Pol. J. Chem., 1981, vol. 55, no. 11, p. 2407. 239. Leo, A., Hansch, C., and Elkins, D., Chem. Rev., 1971, vol. 71, no. 6, p. 525. 240. Makrlik, E., Coll. Czech. Chem. Comm., 1990, vol. 55, no. 11, p. 2602. 241. Gal, J., Persin, M., and Castelas, B., Can. J. Chem., 1983, vol. 61, no. 6, p. 1189. 242. Chiou, S.T. and Block, J.H., Partition Coefficient. Determination and Estimation, New York: 1986. 243. Korenman Ya.I., Koeffitsienty raspredeleniya organicheskikh soedinenii. Spravochnik (Partition Coefficients of Orgqanic Compounds. Handbook), Voronezh Univ., 1992. 244. Lee, W.H. and Wheaton, R.J., J. Chem. Soc., Faraday Trans. 2, 1978, vol. 74, p. 743. 245. Lee, W.H. and Wheaton, R.J., J. Chem. Soc., Faraday Trans. 2, 1978, vol. 74, p. 1456. 246. Lee, W.H. and Wheaton, R.J., J. Chem. Soc., Faraday Trans. 2, 1979, vol. 75, p. 1128. 247. Niazi, M.S.K., Hassan, A., Khan, M.Z.I., Shah, S.S., and Ali, J., J. Chem. Eng. Data., 1992, vol. 37, no. 4, p. 70. 248. Niazi, M.S.K., Shah, S.S., and Khan, M.Z.I., J. Chem. Eng. Data, 1993, vol. 38, no. 2, p. 288. 249. Muinasmaa, U., Rfols, C., Bosch, E., and Ross, M., Anal. Chim. Acta, 1997, vol. 340, p. 133. 250. Karapetyan, Yu.A. and Eichis, V.N., Fiziko-
1887
khimicheskie svoistva elektrolitnykh nevodnykh rastvorov (Physicochemical Properties of Electrolytic Non-Aqueous Solutions), Moscow: Khimiya, 1989. 251. Fuoss, R., J. Phys. Chem., 1978, vol. 82, p. 2427. 252. Salomon, M. and Uchiyama, M.C., J. Solution Chem., 1987, vol. 16, p. 21. 253. Chen, Z. and Hojo, M., J. Phys. Chem., B., 1997, vol. 101, p. 10896. 254. Hojo, M., Pure Appl. Chem., 2008, vol. 80, no. 7, p. 1539. 255. Mchedlov-Petrossyan, N.O., Palval, I.N., Lebed, A.V., and Nikiforova, E.M., J. Mol. Liquids, 2008, vol. 145, no. 3, p. 158. 256. Nakahara, M. and Ibuki, K., J. Phys. Chem., 1986, vol. 90, no. 13, p. 3026. 257. Fialkov, Yu.Ya. and Zhitomirskii, A.N., Zh. Fiz. Khim., 1987, vol. 61, no. 2, p. 390. 258. Krishnam Raju, U.G., Sethuram, B., and Navaneeth Rao, T., Rev. Roumaine de Chimie, 1985, vol. 30, nos. 11 12, p. 941. 259. French, C.M. and Roe, I.G., Trans. Faraday Soc., 1953, vol. 49, p. 314. 260. Hammett, L., Osnovy fizicheskoi organicheskoi khimii (Basics of Physical Organic Chemistry), Moscow: Mir, 1972. 261. Bershtein, I.Ya. and Kaminskii, Yu.L., Spektrofotometricheskii analiz v organicheskoi khimii (Spectrophotometric Analysis in Organic Chemistry), Leningrad: Khimiya, 1986. 262. Meloun, M. and Havel, J., Computation of Solution Equilibria. 1. Spectrophotometry, Brno: Univerzita, 1985. 263. Perrin, D.D., Austr. J. Chem., 1963, vol. 16, no. 4, p. 572. 264. Pustovar, P.Ya., Gershuns, A.L., and Komar, N.P., Zh. Fiz. Khim., 1977, vol. 51, no. 1, p. 206. 265. Sager, E.E., Keegan, H.J., and Acree, S.F., J. Res. NBS, 1943, vol. 31, p. 323. 266. Yamazaki, H., Sperline, R.P., and Freiser, H., Anal. Chem., 1992, vol. 64, no. 22, p. 2720. 267. Robinson, R.A. and Biggs, A.I., Austr, J. Chem., 1957, vol. 10, p. 128. 268. Sager, E.E., Scholley, M.R., Carr, A.S., and Acree, S.F., J. Res. NBS, 1945, vol. 35, p. 521. 269. Mchedlov-Petrosyan, N.O., Kukhtik, V.I., and Egorova, S.I., Zh. Obshch. Khim., 2006, vol. 76, no. 10, p. 1677. 270. Frans, S.D. and Harris, J.M., Anal. Chem., 1985, vol. 57, no. 13, p. 2880. 271. Sergeev, G.B., Batyuk, V.A., Saprykina, T.N., Sergeev, B.M., and Grigoreva, D.N., Vestnik Mosk. Gos. Univ., Ser. Khimiya, 1977, vol. 18, no. 1, p. 47.
1888
ZEVATSKII et al. Soc., 1956, vol. 78, no. 1, p. 1. 296. Kolthoff, I.M., Stcesoc, D., and Lee, T.S., J. Am. Chem. Soc., 1953, vol. 75, no. 8, p. 1834. 297. Moore, F.J. and Johns, J.B., J. Am. Chem. Soc., 1941, vol. 63, p. 3336. 298. Guggenheim, E.A., J. Phys. Chem., 1930, vol. 34, p. 1758. 299. Buck, R.P., Rondinini, S.A. Covington, K., Baucke, F.G.K., Brett, C.M.A., Camkhes, M.F.M., Milton, J.T., Mussini, T., Pratt, R.K.W., Spitzer, P., and Wilson, G.S., Pure Appl. Chem., 2002, vol. 74, no. 11, p. 2169. 300. Mussini, T., Covington, A.K., Longhi, P., and Rondinini, S., Pure. Appl. Chem., 1985, vol. 57, no. 6, p. 865. 301. Aleksandrov, V.V., Berezhnaya, T.A., Borodenko, V.I., and Kabakova, E.N., Khim. Fiz., 1996, vol. 15, no. 11, p. 83. 302. Bykova, L.N., Zh. Analit. Khim., 1971, vol. 26, no. 2, p. 224. 303. Bykova, L.N. and Petrov, S.I., Zh. Analit. Khim., 1972, vol. 27, no. 6, p. 1076. 304. Mussini, P.R., Mussini, T., and Rondinini, S., Pure Appl. Chem., 1997, vol. 69, no. 5, p. 1007. 305. Mussini, T., Covington, A.K., Longhi, P., and Rondinini, S., Pure Appl. Chem., 1987, vol. 59, no. 11, p. 1549. 306. Mollin, J., Chem. Listy, 1988, vol. 82, p. 785; Rondinni, S. and Nese, A., Electrochim. Acta, 1987, vol. 32, no. 10, p. 1499. 307. Strnski, Z. and Kozkov, E., Chem. Listy, 1979, vol. 73, no. 4, p. 337. 308. Kozakova, E., Majersky, P., and Palka, J., Chem. Papers, 1986, vol. 40, no. 4, p. 543. 309. Mchedlov-Petrosyan, N.O. and Vasetskaya, L.V., Zh. Obshch. Khim., 1989, vol. 59, no. 3, p. 691. 310. Mchedlov-Petrosyan, N.O., and Lyubchenko, I.N., Zh. Obshch. Khim., 1987, vol. 57, no. 6, p. 1371. 311. Wrbel, R. and Chmurzyski, L., Anal. Chim. Acta, 2000, vol. 405, p. 303. 312. Pytela, O. and Kulhanek, J., Coll. Czech Chem. Commun., 2002, vol. 67, no. 5, p. 596. 313. Oszczapowich, J. and Czurylowska, M., Talanta, 1984, vol. 31, no. 7, p. 559. 314. Breant, M., Aurox, A., and Lavergne, M., Anal. Chim. Acta, 1976, vol. 83, no. 1, p. 49. 315. Mchedlov-Petrosyan, N.O., Salinas Maiorga, R., and Surov, Yu.N., Zh. Obshch. Khim., 1991, vol. 61, no. 1, p. 225. 316. Mchedlov-Petrossyan, N.O. and Salinas Mayorga, R., J. Chem. Soc., Faraday Trans., 1992, vol. 88, p. 3025. 317. Boni, K.A. and Strobel, H.A., J. Phys. Chem., 1966, vol. 70, no. 12, p. 3771.
272. Nrgaard, L., Anal. Chim. Acta, 1991, vol. 255, p. 143. 273. Tackacs-Novak, K. and Tam, K.Y., J. Pharm. Biomed, Anal., 2000, vol. 21, no. 12, p. 1171. 274. Tackacs-Novak, K. and Tam, K.Y., Spectra Analyse, 2000, vol. 213, p. 33. 275. Reilley, C.N. and Smith, E., M., Anal. Chem., 1960, vol. 33, no. 10, p. 1233. 276. Cacho, J., Garnica, A., and Nerin, C., Anal. Chim. Acta, 1984, vol. 162, p. 113. 277. Ivanov, V.M. and Mamedova, A.M., Vestnik Mosk. Gos. Univ., Ser. Khimiya, 2002, vol. 43, no. 3, p. 167. 278. Ivanov, V.M. and Kuznetsova, O.V., Usp. Khim., 2001, vol. 70, no. 5, p. 411. 279. Fernandez, M.S. and Fromherz, P., J. Phys. Chem., 1977, vol. 81, no. 18, p. 1755. 280. Kubista, M., Ismail, I.H., Forootan, A., and Sjgren, B., J. Fluorescence, 2004, vol. 14, no. 2, p. 139. 281. Libbey, A.J. and Stock, J.T., Anal. Chem., 1970, vol. 42, no. 4, p. 526. 282. Mchedlov-Petrosyan, N.O., Melnik, V.V., Nikishina, L.E., Malinovskii, A.N., and Golota, O.Yu., Zh. Fiz. Khim., 1980, vol. 54, no. 3, p. 654. 283. Tolmachev, V.N., Boberov, O.F., and Lavrushin, V.F., Zh. Obshch. Khim., 1965, vol. 35, no. 12, p. 1841. 284. Gronert, S. and Streitwieser, A., J. Am. Chem. Soc., 1986, vol. 108, no. 22, p. 7016. 285. Kaufman, M.J., Gronert, S., Bors, D.A., and Streitwieser, A., J. Am. Chem. Soc., 1987, vol. 109, no. 2, p. 602. 286. Kaufman, M.J. and Streitwieser, A., J. Am. Chem. Soc., 1987, vol. 109, no. 20, p. 6092. 287. Gronert, S. and Streitwieser, A., J. Am. Chem. Soc., 1988, vol. 110, no. 9, p. 2836. 288. Antipin, I.S., Vedernikov, A.N. and Konovalov, A.I., Zh. Org. Khim., 1985, vol. 21, no. 9, p. 1355. 289. Antipin, I.S., Vedernikov, A.N. and Konovalov, A.I., Zh. Org. Khim., 1986, vol. 22, no. 6, p. 446. 290. Antipin, I.S., Vedernikov, A.N., Solomonov, B.N. and Konovalov, A.I., Zh. Org. Khim., 1988, vol. 24, no. 63, p. 664. 291. Konovalov, A.I. and Antipin, I.S., Metalloorg. Khim., 1989, vol. 2, no. 1, p. 177. 292. Antipin, I.S., Gareyev, R.F., Vedernikov, A.N., and Konovalov, A.I., J., Phys. Org. Chem., 2004, vol. 7, no. 4, p. 181. 293. Kaljurand, I., Rodima, T., Pihl, A., Maemets, V., Leito, I., Koppel, I.A., and Mishima, M., J. Org. Chem., 2003, vol. 68, p. 9988. 294. Garrido, G., Koort, E., Rafols, C., Bosch, E., Rodima, T., Leito, I., and Roses, M., J. Org. Chem. 2006, vol. 71, p. 9062. 295. Kolthoff, I.M. and Bruckenstein, S., J. Am. Chem.
CONTHEMPORARY METHODS FOR THE EXPERIMENTAL DETERMINATION 318. Sysoeva, S.G., Kislina, I.S. and Vinnik, M.I., Izv. Akad. Nauk SSSR, 1987, no. 12, p. 2711. 319. Bowden, K., Chem. Rev., 1966, vol. 66, no. 2, p. 119. 320. Bowden, K. and Stewart, R., Tetrahedron, 1965, vol. 21, p. 261. 321. Langford, C.H. and Burwell, R.L., J. Am. Chem. Soc., 1960, vol. 82, no. 4, p. 1503. 322. Pouw, T.J.M., Bover, W.J., and Zuman, P.T.J., Acidity Functions in Solutions of Strong Bases in Mixed
1889
Solvents, ch. 22, p. 343; Advances in Chemistry, 1976, vol. 155. 323. Steiner, E.C. and Gilbert, J.M., J. Am. Chem. Soc., 1963, vol. 85, p. 3054. 324. Steiner, E.C. and Gilbert, J.M., J. Am. Chem. Soc., 1965, vol. 87, no. 2, p. 382. 325. Poole, S.K., Patel, S., Dehring, K., Workman, H., and Poole, C.F., J. Chromatogr., A, 2004, vol. 1037, p. 445.

Contemporary Methods For The Experimental Determination of Dissociation Constants of Organic Acids in Solutions - Russs - J - Gen - Chen

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ISSN 1070-3632, Russian Journal of General Chemistry, 2009, Vol. 79, No. 9, pp. 18591889. Pleiades Publishing, Ltd.

ZEVATSKII et al. Scheme 1. HAMn + mM HA + (n + m)M H+ + A Hsolv + A + xM solv solv solv

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 9 2009

CONTHEMPORARY METHODS FOR THE EXPERIMENTAL DETERMINATION

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 9 2009

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 9 2009

DN 29.8 26.6 14.1 17.0 15.1 2.7

log ws H 0 +1.52 +1.94 3.40 2.52 +7.85 7 6.58.8

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 9 2009

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 9 2009

CONTHEMPORARY METHODS FOR THE EXPERIMENTAL DETERMINATION

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 9 2009

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 9 2009

CONTHEMPORARY METHODS FOR THE EXPERIMENTAL DETERMINATION

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 9 2009

cHA[Cl] (E E0)F . + log 2.303RT cCA

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 9 2009

CONTHEMPORARY METHODS FOR THE EXPERIMENTAL DETERMINATION

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 9 2009

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 9 2009

CONTHEMPORARY METHODS FOR THE EXPERIMENTAL DETERMINATION

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 9 2009

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 9 2009

CONTHEMPORARY METHODS FOR THE EXPERIMENTAL DETERMINATION

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 9 2009

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 9 2009

CONTHEMPORARY METHODS FOR THE EXPERIMENTAL DETERMINATION

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 9 2009

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 9 2009

CONTHEMPORARY METHODS FOR THE EXPERIMENTAL DETERMINATION

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 9 2009

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 9 2009

CONTHEMPORARY METHODS FOR THE EXPERIMENTAL DETERMINATION

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 9 2009

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 9 2009

CONTHEMPORARY METHODS FOR THE EXPERIMENTAL DETERMINATION

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 9 2009

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 9 2009

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 9 2009

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 9 2009

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 9 2009

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 9 2009

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 9 2009

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 9 2009

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 9 2009

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